Non-aqueous absorbent and use thereof

ABSTRACT

A non-aqueous absorbent comprising a crosslinked polymer which contains a structural unit having a carboxyl group and/or a sulfonate group in an amount of 20 to 100% weight in its molecule and in which from 30 to 100% by mol of the protons in the carboxyl group and/or the sulfonate group have been substituted by onium cations; a non-aqueous gel made of this non-aqueous absorbent and an organic solvent; and a non-aqueous absorbent sheet and a non-aqueous absorbent agent containing the non-aqueous absorbent. Because of having excellent capabilities of absorbing and holding various organic solvents such as alcohols and gelating, these materials are usable for various purposes, for example, lithium batteries, alcohol-based bactericidal materials or alcohol-based bactericides, cold insulating materials or cold insulators, gel sheets for cooling, fuel compositions for solid fuels or solid fuels using the same, fragrance materials or fragrances, patch materials or patches, insecticidal compositions or insecticides, fuel stores for fuel batteries or fuel batteries using the same.

TECHNICAL FIELD

The present invention relates to a non-aqueous absorbent comprising acrosslinked body having a particular composition, and a non-aqueousabsorbing gel, a non-aqueous absorbing sheet and a non-aqueous absorbentagent using the same. More particularly, the present invention relatesto a non-aqueous absorbent having extremely high capabilities ofabsorbing and gelating an organic solvent, and a form such as anon-aqueous absorbing gel, a non-aqueous absorbing sheet, a non-aqueousabsorbent agent and the like, as well as various uses employing them.

BACKGROUND TECHNIQUE

Previously, a crosslinked sodium polyacrylate salt has been used as awater-absorbing resin in a variety of utilities. However, in thiscomposition, an amount of absorbing water or urine is high, but a resinis not swollen at all in an organic solvent. Therefore, the resin is notapplied as an agent for absorbing an organic solvent or as a gelatingagent.

As a crosslinked resin which absorbs an organic solvent, for example,there are proposed:

-   -   (1) a crosslinked polymer of a monomer containing a tertiary or        quaternary amino group such as dialkylaminoalkyl(meth)acrylate,        (meth)acryloyltrialkylammonium chloride and the like (JP-A No.        58-154709 gazette),    -   (2) an alcohol absorbent comprising a crosslinked copolymer of        the aforementioned tertiary amino group-containing monomer and a        vinyl monomer having a carboxyl group (JP-A No. 60-179410        gazette, JP-A No. 60-192717 gazette etc.),    -   (3) an oil absorbent comprising crosslinked (meth)acrylate of a        monovalent aliphatic alcohol having a carbon number of 10 to 16        or a crosslinked monomer having a solubility parameter of 9 or        smaller (JP-A No. 3-221582 gazette, JP-No. 4-100539 gazette        etc.),    -   (4) a liquid-absorbing resin comprising crosslinked alkoxyalkyl        (meth)acrylate and the like or crosslinked N-vinyllactam (JP-A        No. 10-101745 gazette, JP-A No. 11-35632 gazette etc.),    -   (5) a liquid-absorbing resin comprising crosslinked        N-vinylacetamide (JP-A No. 4-230250 gazette, JP-A No. 8-59743        gazette).

In addition, in the fields of lithium batteries and condensers, a polarorganic solvent such as propylene carbonate and γ-butyrolactone isusually used as an electrolyte solution. In order to make a battery thinor to prevent solution leakage at damage, there is a great demand forgelating this organic solvent. As a polymer for gelating an electrolytesolution, for example, there are proposed:

-   -   (6) crosslinked polyalkylene oxide (hereinafter, referred to as        PEO system, JP-A No. 62-285954 gazette, JP-A No. 6-68906 gazette        and many publications),    -   (7) crosslinked polyacrylnitrile (hereinafter, referred to as        PAN system, JP-A No. 8-264205 gazette, JP-A No. 2000-58078        gazette, JP-A No. 2000-223105 gazette etc.),    -   (8) crosslinked polyacrylic acid ester, and    -   a method of using a polymer having the same composition as that        of the (1) as a gelating agent for an electrolyte solution (JP-A        No. 2000-331533 gazette, 2001-123073 gazette etc.).

However, although the crosslinked polymer of (1) exhibits a relativelyhigh amount of absorbing an alcohol, the polymer has a low amount ofabsorbing an organic solvent other than an alcohol, for example,propylene carbonate, γ-butyrolactone, toluene and the like, and at thesame time, an ester group of this kind of cationic polymer is extremelyeasily degraded at a region of a pH 4 or larger due to intramolecularinteraction between an amino group and an ester group, and therefore,there is a problem that the polymer is not suitable for utilitiesrequiring durability of a polymer, such as a gelating agent for anelectrolyte solution.

In addition, regarding crosslinked polymers of (3) to (8), since thesepolymers are fundamentally a nonionic polymer, dissociation of a polymerdoes not occur in the aforementioned subject organic solvents.Therefore, those polymers have weak capabilities of absorbing andgelating subject organic solvents and, in order to absorb and gelatethese organic solvents, it becomes necessary to add a large amount of apolymer. There is a problem that not only this is uneconomical, but alsowhen used in utilities such as batteries and condensers, addition of alarge amount of a polymer reduces an electrical conductivity of anelectrolyte solution, and deteriorates electrical properties.

Further, lithium batteries and condensers are used in mobile phones,computers, various appliance products and the like. However, there is aproblem that, when an organic solvent-based electrolyte solution isleaked, a harmful gas is generated, substrates of other ICs andsemiconductors are polluted, and ignition occurs in some cases.Regarding prevention of leakage of these electrolyte solutions, only anon-woven fabric sheet is practically proposed. The non-woven fabric hasan extremely small solution holding amount to these electrolytesolutions. When there is a great leakage, this can not be defended atall. Therefore, there is a great demand for development of a sheet whichcan hold a large amount of these organic solvents.

In view of the aforementioned circumstances, the present inventorsintensively studied, and as a result, found that a non-aqueous absorbentcomprising a crosslinked body having a particular composition hasextremely high capabilities of absorbing and gelating the aforementionedorganic solvents, a large amount of organic solvents can be absorbed andgelated by addition of a small amount of the non-aqueous absorbent, anda sheet containing the non-aqueous absorbent has an extremely highamount of holding the aforementioned organic solvents, and can hold alarge amount of those organic solvents, which resulted in completion ofthe present invention.

An object of the present invention is to provide a non-aqueous absorbentwhich has extremely high capabilities of absorbing and gelating organicsolvents, and can absorb a large amount of organic solvent and gelateorganic solvents by addition of a small amount of the same.

Another object of the present invention is to provide various uses ofthis non-aqueous absorbent in various forms.

SUMMARY OF THE INVENTION

That is, the present invention is a non-aqueous absorbent (B) comprisinga crosslinked polymer (1) (A) which contains a structural unit having acarboxyl group and/or a sulfonate group in an amount of 20 to 100% byweight in its molecule and in which from 30 to 100% by mol of theprotons in the carboxyl group and/or the sulfonate group have beensubstituted by onium cations; a form of non-aqueous gel (C), anon-aqueous absorbent sheet (D) and a non-aqueous absorbent agent (E)made of the (B); as well as uses of an alcohol-based bactericidalmaterial or an alcohol-based bactericide, a cold insulating material ora cold insulator, a gel sheet for cooling, a fuel composition for solidfuels or a solid fuel using the same, a fragrance material or afragrance, a patch material or a patch, an insecticidal composition oran insecticide, a fuel store for fuel batteries or a fuel battery usingthe same, or a lithium battery or the like.

BEST MODE FOR CARRYING OUT THE INVENTION

The non-aqueous absorbent (B) of the present invention is characterizedin that it comprises a crosslinked polymer (1) (A) which contains apredetermined amount of a structural unit having a carboxyl group and/ora sulfonate group in its molecule, and in which protons of the carboxylgroup and/or the sulfonate group are substituted with a predeterminedamount of onium cations, for the purpose of absorbing gelating subjectorganic solvents. That is, the non-aqueous absorbent (B) of the presentinvention comprises a crosslinked polymer (1) (A) which contains astructural unit having a carboxyl group and/or a sulfonate group in anamount of 20 to 100% by weight in its molecule, and in which from 30 to100% by mole of protons of the carboxyl group and/or the sulfonate groupare substituted with onium cations.

Examples of a monomer (a′) constituting a structural unit (a) having acarboxyl group and/or a sulfonate group include carboxylgroup-containing monomers [e.g. (meth)acrylic acid, (eth)acrylic acid,crotonic acid, sorbic acid, maleic acid, itaconic acid, fumaric acid,cinnamic acid, and anhydride thereof etc.]; sulfonate group-containingmonomers [e.g. aliphatic vinyl sulfonic acid [vinyl sulfonic acid,allylsulfonic acid, vinyl toluenesulfonic acid, styrenesulfonic acid,etc.], (meth)acrylate-type sulfonic acid [sulfoethyl(meth)acrylate,sulfopropyl(meth)acrylate etc.] and (meth)acryl amide-type sulfonic acid[acrylamido-2-methylpropanesulfonic acid etc.]], and one or more polymer(1). Preferable is a structural unit having a carboxyl group and/or asulfonate group having a carbon number of 3 to 30.

In addition, examples of a method of obtaining a polymer (1) containinga predetermined amount of a structural unit having a carboxyl groupand/or a sulfonate group in its molecule include, in addition to themethod of polymerizing a predetermined amount of a monomer (a′)constituting the structural unit (a), a method of polymerizing a monomerwhich can be easily converted into a carboxyl group and/or a sulfonategroup such as an ester and an amide of the carboxyl group and/orsulfonate group-containing monomer, and introducing a predeterminedamount of a structural unit of a carboxyl group or a sulfonate groupinto a molecule using such as a hydrolyzing method, and a method ofobtaining a carboxyl group or sulfonate group-containing polysaccharidepolymer, a representative of which is carboxymethylcellulose, or a graftcopolymer of the polysaccharide and other monomer. However, such themethod is not particularly limited as long as a polymer containing apredetermined amount of a structural unit of a carboxyl group and/or asulfonate group is finally obtained.

In the present invention, it is necessary that a content of the polymer(1) of a structural unit (a) having a carboxyl group and/or a sulfonategroup is 20 to 100% by weight, preferably 40 to 100% by weight, morepreferably 60 to 100% by weight based on a weight of the polymer (1).When the content is smaller than 20% by weight, an amount of absorbing asubject organic solvent is reduced, or a subject organic solvent can notbe gelated at a small amount in some cases, even when protons ofcarboxylic acid or sulfonic acid are substituted with onium cationsdescribed later.

In the present invention, examples of a copolymerizable monomer (b′)constituting a structural unit other than a structural unit (a) having acarboxyl group and/or a sulfonate group include alkyl(meth)acrylate(carbon number 1 to 30) esters [methyl (meth)acrylate,ethyl(meth)acrylate, propyl(meth)acrylate, butyl (meth)acrylate,ethylhexyl(meth)acrylate, octyl(meth)acrylate, dodecyl(meth)acrylate,stearyl(meth)acrylate, cyclohexyl (meth)acrylate, etc.];oxyalkyl(meth)acrylates (carbon number 1 to 4)[hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, (meth)acrylatemono(polyethylene glycol)ester [polyethlene glycol (hereinafter,referred to as PEG) number average molecular weight: 100 to 4,000],(meth)acrylic acid mono(polypropylene glycol)ester [polypropylene glycol(hereinafter, referred to as PPG) number average molecular weight: 100to 4,000], (meth)acrylic acid monomethoxy polyethylene glycol (PEGnumber average molecular weight: 100 to 4,000), (meth)acrylic acidmonomethoxy propylene glycol (PPG number average molecular weight: 100to 4,000) etc.], (meth)acrylamides [(meth)acrylamide,(di)methyl(meth)acrylamide, (di)ethyl(meth)acrylamide,(di)propyl(meth)acrylamide etc.]; allyl ethers [methyl allyl ether,ethyl allyl ether, propyl allyl ether, glycerol monoallyl ether,trimethylolpropane triallyl ether, pentaerythritol monoallyl ether,etc.]; α-olefins having a carbon number of 4 to 20 [isobutylene,1-hexene, 1-octene, iso-octene, 1-nonene, 1-decene, 1-dodecene etc.];aromatic vinyl compounds having a carbon number of 8 to 20 [styrene,t-butylstyrene, octylstyrene etc.]; other vinyl compounds[N-vinylacetamide, vinyl caproate, vinyl laurate, vinyl stearate etc.],amino group-containing monomers [dialkyl(carbon number of alkyl: 1 to5)aminoethyl(meth)acrylate, meth(acryloyl)oxyethyltrialkyl(carbon numberof alkyl: 1 to 5)ammonium chloride, bromide or sulfate etc.] and alkalimetal salts, primary to tertiary amine salts or alkanolamine salts ofthe aforementioned monomers having a carboxyl group or a sulfonategroup. It is preferable that one or more of these monomers (b′) is (are)copolymerized with the (a′) in a range of a predetermined amount(smaller than 80% of polymer structural unit) as necessary.

From a viewpoint of polymerizability of a monomer and stability of theproduced polymer, among the aforementioned monomers (b′),alkyl(meth)acrylate esters, oxyalkyl(meth)acrylates, allyl ethers,α-olefins, and aromatic vinyl compounds are preferable.

In addition, since the present invention is aimed at absorbing andgelating various organic solvents, it is preferable to select such amonomer (b′) that a difference between a SP value (solubility parameter)of an organic solvent and that of a monomer (b′) is 5 or smaller,depending on a SP value of a subject organic solvent because anabsorbing amount and a gelating capability are easily increased. It ismore preferable to select such a monomer (b′) that a difference of a SPvalue of a subject organic solvent and that of the monomer (b′) is 3 orsmaller.

In the present invention, it is essential that from 30 to 100% by mol ofprotons of the carboxyl group and/or the sulfonate group are substitutedwith onium cations.

The onium cation is one or more selected from the group consisting ofquaternary ammonium cation (I), tertiary sulfonium cation (II),quaternary phosphonium cation (III) and tertiary oxonium cation (IV).

Examples of the quaternary ammonium cation (I) include the following(I-1) to (I-11) (hereinafter, cation is omitted).

(I-1) Aliphatic quaternary ammoniums having an alkyl and/or alkenylgroup having a carbon number of 4 to 30 or more;

-   tetramethylammonium, ethyltrimethylammonium,    diethyldimethylammonium, triethylmethylammonium, tetraethylammonium,    trimethylpropylammonium, dimethylpropylammonium,    ethylmethyldipropylammonium, tetrapropylammonium,    butyltrimethylammonium, dimethyldibutylammonium, tetrabutylammonium,    etc.;

(I-2) Aromatic quaternary ammoniums having a carbon number of 6 to 30 ormore; trimethylphenylammonium, dimethylethylphenylammonium,triethylphenylammonium, etc.;

(I-3) Alicyclic quaternary ammoniums having a carbon number of 3 to 30or more; N,N-dimethylpyrrolidinium, N-ethyl-N-methylpyrrolidinium,N,N-diethylpyrrolidinium, N,N-dimethylmorpholinium,N-ethyl-N-methylmorpholinium, N,N-diethylmorpholinium,N,N-dimethylpiperidinium, N,N-diethylpiperidinium etc.;

(I-4) Imidazoliniums having a carbon number of 3 to 30 or more;

-   1,2,3-trimethylimidazolinium, 1,2,3,4-tetramethylimidazolinium,    1,3,4-trimethyl-2-ethylimidazolinium,    1,3-dimethyl-2,4-diethylimidazolinium,    1,2-dimethyl-3,4-diethylimidazolinium,    1,2-dimethyl-3-ethylimidazolinium, 1-ethyl-3-methylimidazolinium,    1-methyl-3-ethylimidazolinium, 1,2,3,4-tetraethylimidazolinium,    1,2,3-triethylimidazolinium, 4-cyano-1,2,3-trimethylimidazolinium,    2-cyanomethyl-1,3-dimethylimidazolinium,    4-acetyl-1,2,3-trimethylimidazolinium,    3-acetylmethyl-1,2-dimethylimidazolinium,    4-methylcarboxymethyl-1,2,3-trimethylimidazolinium,    3-methoxy-1,2-dimethylimidazolinium,    4-formyl-1,2,3-trimethylimidazolinium,    4-formyl-1,2-dimethylimidazolinium,    3-hydroxyethyl-1,2,3-trimethylimidazolinium,    3-hydroxyethyl-1,2-dimethylimidazolinium, etc.;

(I-5) Imidazoliums having a carbon number of 3 to 30 or more;

-   1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium,    1-methyl-3-ethylimidazolium, 1,2,3-trimethylimidazolium,    1,2,3,4-tetramethylimidazolium, 1,3-dimethyl-2-ethylimidazolium,    1,2-dimethyl-3-ethylimidazolium, 1-ethyl-3-methylimidazolium,    1-methyl-3-ethylimidazolium, 1,2,3-triethylimidazolium,    1,2,3,4-tetraethylimidazolium, 1,3-dimethyl-2-phenylimidazolium,    1,3-dimethyl-2-benzylimidazolium, 1-benzyl-2,3-dimethylimidazolium,    4-cyano-1,2,3-trimethylimiddazolium,    3-cyanomethyl-1,2-dimethylimidazolium,    4-acetyl-1,2,3-trimethylimidazolium,    3-acetylmethyl-1,2-dimethylimidazolium,    4-carboxymethyl-1,2,3-trimethylimidazolium,    3-methylcarboxymethyl-1,2-dimethylimidazolium,    4-methoxy-1,2,3-trimethylimidazolium,    4-formyl-1,2,3-trimethylimidazolium,    3-formylmethyl-1,2-dimethylimidazolium,    3-hydroxyethyl-1,2-dimethylimidazolium,    2-hydroxyethyl-1,3-dimethylimidazolium,    N,N′-dimethylbenzimidazolium, N,N′-diethylbenzimidazolium,    N-methyl-N′-ethylbenzimidazolium, etc.;

(I-6) Tetrahydropyrimidinium having a carbon number of 4 to 30 or more;

-   1,3-dimethyltetrahydropyrimidinium,    1,2,3-trimethyltetrahydropyrimidinium,    1,2,3,4-tetramethyltetrahydropyrimidinium,    8-methyl-1,8-diazabicyclo[5,4,0]-7-undecenium,    5-methyl-1,5-diazabicyclo[4,3,0]-5-nonenium,    4-cyano-1,2,3-trimethyltetrahydropyrimidinium,    3-cyanomethyl-1,2-dimethyltetrahydropyrimidinium,    4-acetyl-1,2,3-trimethyltetrahydropyrimidinium,    3-acetylmethyl-1,2-dimethyltetrahydropyrimidinium,    4-methylcarboxymethyl-1,2,3-trimethyl-tetrahydropyrimidinium,    4-methoxy-1,2,3-trimethyltetrahydropyrimidinium,    3-methoxymethyl-1,2-dimethyltetrahydropyrimidinium,    4-hydroxymethyl-1,2,3-trimethyltetrahydropyrimidinium,    4-hydroxymethyl-1,3-dimethltetrahydropyrimidinium, etc.;

(I-7) Dihydropyrimidiniums having a carbon number of 4 to 30 or more;

-   1,3-dimethyl-2,4- or-2,6-dihydropyrimidinium, [these are expressed    by 1,3-dimethyl-2,4,(6)-dihydropyrimidinium, and the similar    expression is used hereinafter],    1,2,3-trimethyl-2,4,(6)-dihydropyrimidinium,    1,2,3,4-tetramethyl-2,4,(6)-dihydropyrimidinium,    1,2,3,5-tetramethyl-2,4,(6)-dihydropyrimidinium,    8-methyl-1,8-diazacyclo[5,4,0]-7,9(10)-undecadienium,    5-methyl-1,5-diazacyclo[4,3,0]-5,7(8)-nonadienium,    2-cyanomethyl-1,3-dimethyl-2,4,(6)-dihydropyrimidinium,    3-acetylmethyl-1,2-dimethyl-2,4,(6)-dihydropyrimidinium,    4-methylcarboxymethyl-1,2,3-trimethyl-2,4,(6)-dihydropyrimidinium,    4-methoxy-1,2,3-trimethyl-2,4, (6)-dihydropyrimidinium,    4-formyl-1,2,3-trimethyl-2,4,(6)-dihydropyrimidinium,    3-hydroxyethyl-1,2-dimethyl-2,4, (6)-dihydropyrimidinium,    2-hydroxyethyl-1,3-dimethyl-2,4,(6)-dihydropyrimidinium, etc.;

(I-8) Guanidiums having an imidazolinium skeleton having a carbon numberof 3 to 30 or more;

-   2-dimethylamino-1,3,4-trimethylimidazolinium,    2-diethylamino-1,3,4-trimethylimidazolinium,    2-diethylamino-1,3-dimethyl-4-ethylimidazolinium,    2-dimethylamino-1-methyl-3,4-diethylimidazolinium,    2-diethylamino-1,3,4-triethylimidazolinium,    2-dimethylamino-1,3-dimethylimidazolinium,    2-diethylamino-1,3-dimethylimidazolinium,    2-diethylamino-1,3-diethylimidazolinium,    1,5,6,7-tetrahydro-1,2-dimethyl-2H-imido[1,2a]imidazolinium,    1,5,6,7-tetrahydro-1,2-dimethyl-2H-pyrimido[1,2a]imidazolinium,    1,5-dihydro-1,2-dimethyl-2H-pyrimido[1,2a]imidazolinium,    2-dimethyl-3-cyanomethyl-1-methylimidazolinium,    2-dimethylamino-3-methylcarboxymethyl-1-methylimidazolinium,    2-dimethylamino-4-formyl-1,3-dimethylimidazolinium,    2-dimethylamino-3-hydroxyethyl-1-methylimidazolinium,    2-dimethylamino-4-hydroxymethyl-1,3-dimethylimidazolinium, etc.;

(I-9) Guanidiums having an imidazolium skeleton having a carbon numberof 3 to 30 or more;

-   2-dimethylamino-1,3,4-trimethylimidazolium,    2-diethylamino-1,3,4-trimethylimidazolium,    2-diethylamino-1,3-dimethyl-4-ethylimidazolium,    2-diethylamino-1-methyl-3,4-diethylimidazolium,    2-diethylamino-1,3,4-triethylimidazolium,    2-diemethylamino-1,3-dimethylimidazolium,    2-dimethylamino-1-ethyl-3-methylimidazolium,    2-diethylamino-1,3-diethylimidazolium,    1,5,6,7-tetrahydro-1,2-dimethyl-2H-imido[1,2a]imidazolium,    1,5,6,7-tetrahydro-1,2-dimethyl-2H-pyrimido[1,2a]imidazolium,    1,5-dihydro-1,2-dimethyl-2Hpyrimido-[1,2a]imidazolium,    2-dimethylamino-3-cyanomethyl-1-methylimidazolium,    2-dimethylamino-acetyl-1,3-dimethylimidazolium,    2-dimethylamino-4-methylcarboxymethyl-1,3-dimethylimidazolium,    2-dimethylamino-4-methoxy-1,3-dimethylimidazolium,    2-dimethylamino-3-methoxymethyl-1-methylimidazolium,    2-dimethylamino-3-formylmethyl-1-methylimidazolium,    2-dimethylamino-4-hydroxymethyl-1,3-dimethylimidazolium etc.;

(I-10) Guanidiums having a tetrahydropyrimidinium skeleton having acarbon number of 4 to 30 or more;

-   2-dimethylamino-1,3,4-trimethyltetrahydropyrimidinium,    2-diethylamino-1,3,4-trimethyltetrahydropyrimidinium,    2-diethylamino-1,3-dimethyl-4-ethyltetrahydropyrimidinium,    2-diethylamino-1-methyl-3,4-diethyltetrahydropyrimidinium,    2-dimethylamino-1,3-dimethyltetrahydropyrimidinium,    2-diethylamino-1,3-dimethyltetrahydropyrimidinium,    2-diethylamino-1,3-diethyltetrahydropyrimidinium,    1,3,4,6,7,8-hexahydro-1,2-dimethyl-2H-imido[1,2a]pyrimidinium,    1,3,4,6,7,8-hexahydro-1,2-dimethyl-2H-pyrimido[1,2a]pyrimidinium,    2,3,4,6-tetrahydro-1,2-dimethyl-2H-pyrimido[1,2a]pyrimidinium,    2-dimethylamino-3-cyanomethyl-1-methyltetrahydropyrimidinium,    2-dimethylamino-4-acetyl-1,3-dimethyltetrahydropyrimidinium,    2-dimethylamino-4-methylcarboxymethyl-1,3-dimethyltetrahydropyrimidinium,    2-dimethylamino-3-methylcarboxymethyl-1-methyltetrahydropyrimidinium,    2-dimethylamino-3-methoxymethyl-1-methyltetrahydropyrimidinium,    2-dimethylamino-4-formyl-1,3-dimethyltetrahydropyrimidinium,    2-dimethylamino-3-hydroxyethyl-1-methyltetrahydropyrimidinium,    2-dimethylamino-4-hydroxymethyl-1,3-dimethyltetrahydropyrimidinium    etc.;

(I-11) Guanidiums having a dihydropyrimidinium skeleton having a carbonnumber of 4 to 30 or more;

-   2-dimethylamino-1,3,4-trimethyl-2,4(6)-dihydropyrimidinium,    2-diethylamino-1,3,4-trimethyl-2,4(6)-dihydropyrimidinium,    2-dimethylamino-1-methyl-3,4-diethyl-2,4(6)-dihydropyrimidinium,    2-diethylamino-1-methyl-3,4-diethyl-2,4(6)-dihydropyrimidinium,    4-diethylamino-1,3,4-triethyl-2,4(6)-dihydropyrimidinium,    2-diethylamino-1,3-dimethyl-2,4(6)-dihydropyrimidinium,    2-diethylamino-1,3-dimethyl-2,4(6)-dihydropyrimidinium,    2-dimethylamino-1-ethyl-3-methyl-2,4(6)-dihydropyrimidinium,    1,6,7,8-tetrahydro-1,2-dimethyl-2H-imido[1,2a]pyrimidinium,    1,6-dihydro-1,2-dimethyl-2H-imido[1,2a]pyrimidinium,    1,6-dihydro-1,2-dimethyl-2H-pyrimido[1,2a]pyrimidinium,    2-dimethylamino-4-cyano-1,3-dimethyl-2,4(6)-dihydropyrimidinium,    2-dimethylamino-4-acetyl-1,3-dimethyl-2,4(6)-dihydropyrimidinium,    2-dimethylamino-3-acetylmethyl-1-methyl-2,4(6)-dihydropyrimidinium,    2-dimethylamino-3-methylcarboxymethyl-1-methyl-2,4(6)-dihydropyrimidinium,    2-dimethylamino-4-methoxy-1,3-dimethyl-2,4(6)-dihydropyrimidinium,    2-dimethylamino-4-formyl-1,3-dimethyl-2,4(6)-dihydropyrimidinium,    2-dimethylamino-3-formylmethyl-1-methyl-2,4(6)-dihydropyrimidinium,    2-dimethylamino-4-hydroxymethyl-1,3-dimethyl-2,4(6)-dihydropyrimidinium    etc.

Examples of the tertiary sulfonium cation (II) include the following(II-1) to (II-3):

(II-1) Aliphatic tertiary sulfoniums having an alkyl and/or alkenylgroup having a carbon number of 1 to 30 or more;

-   trimethylsulfonium, triethylsulfonium, ethyldimethylsulfonium,    diethylmethylsulfonium etc.;

(II-2) Aliphatic tertiary sulfoniums having a carbon number of 6 to 30or more;

-   phenyldimethylsulfonium, phenylethylmethylsulfonium,    phenylmethylbenzylsulfonium etc.;

(II-3) Alicyclic tertiary phosphoniums having a carbon number of 3 to 30or more;

-   methylthiolanium, phenylthiolanium, methylthianium etc.

Examples of the quaternary phosphonium cation (III) include thefollowing (III-1) to (III-3):

(III-1); Aliphatic quaternary phosphoniums having an alkyl and/oralkenyl group having a carbon number of 1 to 30 or more;

-   tetramethylphosphonium, tetraethylphosphonium,    tetrapropylphosphonium, tetrabutylphosphonium,    methyltriethylphosphonium, methyltripropylphosphonium,    methyltributylphosphonium, dimethyldiethylphosphonium,    dimethyldipropylphosphonium, dimethyldibutylphosphonium,    trimethylethylphosphonium, trimethylpropylphosphonium,    trimethylbutylphosphonium etc.;

(III-2) Aromatic quaternary phosphoniums having a carbon number of 6 to30 or more;

-   triphenylmethylphosphonium, diphenyldimethylphosphonium,    triphenylbenzylphosphonium etc.;

(III-3) Alicyclic quaternary phosphoniums having a carbon number of 3-30or more;

-   1,1-dimethylphosphoranium, 1-methyl-1-ethylphosphoranium,    1,1-diethylphosphoranium, 1,1-dimethylphosphorynanium,    1-methyl-1-ethylphosphorinanium, 1,1-diethylphosphorinanium,    1,1-pentaethylenephosphorinanium etc.

Examples of the tertiary oxonium cation (IV) include the following(IV-1) to (IV-3):

(IV-1) Aliphatic tertiary oxoniums having an alkyl and/or alkenyl grouphaving a carbon number of 1 to 30 or more;

-   trimethyloxonium, triethyloxonium, ethyldimethyloxonium,    diethylmethyloxonium etc.;

(IV-2) Aromatic tertiary oxoniums having a carbon number of 6 to 30 ormore;

-   phenyldimethyloxonium, phenylethylmethyloxonium,    phenylmethylbenzyloxonium etc.;

(IV-3) Alicyclic tertiary oxoniums having a carbon number of 3 to 30 ormore;

-   methyloxolanium, phenyloxolanium, methyloxanium etc.

Among them, preferable onium cation is (I), more preferable are (I-1),(I-4) and (I-5), and further preferable are (I-4) and (I-5).

These onium cations may be used alone or in combination of two or more.

In the present invention, examples of a method of introducing an oniumcation into a polymer include a method of substituting protons of acarboxyl group and/or a sulfonate group of a polymer with the oniumcations. As the method of substituting protons with the onium cations,any methods may be used as long as they are a method which cansubstitute a predetermined amount with the onium cations. For example,protons can be easily substituted by adding a hydroxide salt (e.g.tetraethylammonium hydroxide etc.) or a monomethylcarbonate salt (e.g.1,2,3,4-trimethylimidazolinium monomethylcarbonate salt etc.) of theonium cation to a polymer containing a carboxyl group and/or a sulfonategroup, and performing dehydration, decarbonization or demethanolation asnecessary. Alternatively, substitution may be performed similarly at astage of a monomer.

Regarding a stage of substitution with the onium cations, examplesinclude a method of polymerization after a monomer containing thecarboxyl group and/or the sulfonate group is substituted with the oniumcations, and a method of substituting protons of an acid with the oniumcations after a polymer having a carboxyl group and/or a sulfonate groupis prepared, but substitution may be performed at any stage as long asprotons of a carboxyl group and/or a sulfonate group of a final polymerare substituted.

In the present invention, an degree of substitution (substitutiondegree) of protons of a carboxyl group and/or a sulfonate group with theonium cations is different variously depending on utility of a finalproduct (e.g. utility such as non-aqueous absorbent sheet or non-aqueousabsorbent agent, gelating agent of an electrolyte solution etc.), but asubstitution degree is necessary to be 30 to 100% by mol, preferably 50to 100% by mol, more preferably 70 to 100% by mol. In addition, whenutility is a gelating agent of a lithium battery containing a lithiumsalt, it is particularly preferable that a substitution degree is ashigh as 90 to 100% by mol from a viewpoint of reduction in activeprotons.

When a substitution degree by the onium cations is smaller than 30% bymol, dissociation of a carboxyl group and a sulfonate group of a polymer(1) and an onium cation is too low, therefore, swelling capability andgelating capability are low, and electric properties are reduced due totoo much active protons, in some cases, depending on utility.

In the present invention, the polymer (I) which contains a predeterminedamount of a structural unit having a carboxyl group and/or a sulfonategroup and in which the carboxyl group and/or the sulfonate group issubstituted with a predetermined amount of onium cations, is finallycrosslinked to obtain a crosslinked body.

A crosslinking method may be the known method, and examples include thefollowing (i) to (v) methods:

(i) Crosslinking with copolymerizing crosslinking agent;

A method of performing crosslinking by copolymerizing the carboxyl groupand/or sulfonate group-containing monomer (a′), the monomer substitutedwith an onium cation and, if necessary, a copolymerizing crosslinkingagent which is copolymerizable with other copolymerizable monomer (b′)or has two or more double bonds in a molecule [multivalent vinyl-typecrosslinking agent such as divinylbenzene etc., (meth)acrylamide-typecrosslinking agent such as N,N′-methylenebisacrylamide etc., multivalentallyl ether-type crosslinking agent such as pentaerythritol triallylether etc., multivalent (meth)acrylic acid ester-type crosslinking agentsuch as trimethylolpropane triacrylate etc., etc.].

(ii) Crosslinking with a reactive crosslinking agent;

A method of performing crosslinking using a monomer having a carboxylgroup and/or a sulfonate group or the group substituted with an oniumcation and, if necessary, a reactive crosslinking agent having two ormore functional groups which can react with a functional group of acopolymerizable monomer, in a molecule [multivalent isocyanate-typecrosslinking agent such as 4,4′-diphenylmethane diisocyanate etc.,multivalent epoxy-type crosslinking agent such as polyglycelolpolyglycidyl ether etc., polyhydric alcohol-type crosslinking agent suchas glycerin etc., multivalent amine or imine-type crosslinking agentsuch as hexamethylenetetramine and polyethyleneimine etc.,haloepoxy-type crosslinking agent such as epichlorohydrin etc.,multivalent metal salt-type crosslinking agent such as aluminum sulfateetc., etc.].

(iii) Crosslinking with polymerization reactive crosslinking agent;

A method of performing crosslinking using the carboxyl group and/orsulfonate group-containing monomer (a′), the monomer substituted with anonium cation, a monomer which is copolymerizable with other monomer (b′)to be copolymerized if necessary, or has a double bond in a molecule,and has a carboxyl group and/or a sulfonate group or the groupsubstituted with an onium cation, and a polymerization reactivecrosslinking agent having a functional group which can react with afunctional group of a monomer to be copolymerized if necessary, in amolecule [glycidyl (meth)acrylate-type crosslinking agent of glycidylmethacrylate etc., allylepoxy-type crosslinking agent such as allylglycidyl ether etc., etc.].

(iv) Crosslinking with irradiation;

A method of crosslinking a polymer (1) by irradiating the polymer (1)with radiation such as ultraviolet-ray, electron beam, γ-ray or thelike, and a method of performing polymerization and crosslinking at thesame time by irradiating the monomer with radiation such asultraviolet-ray, electron beam, Tray or the like.

(v) Crosslinking with heating

A method of performing thermal intermolecular crosslinking of a polymer(1) by heating the polymer (1) at 100° C. or higher [crosslinkingbetween carbons or crosslinking between functional groups by generationof a radical by heating].

Among these crosslinking methods, a preferable method is differentdepending on use and a form of a final product, and is (i) (ii) (iv)from an overall viewpoint.

Among the aforementioned copolymerizing crosslinking agents, preferableare a (meth)acrylamide-type crosslinking agent, a multivalent allylether-type crosslinking agent, and a multivalent (meth)acrylic acidester-type crosslinking agent, and more preferable is a multivalentallyl ether-type crosslinking agent.

Among the aforementioned reactive crosslinking agents, preferable are amultivalent isocyanate-type crosslinking agent and a multivalentepoxy-type crosslinking agent, and more preferable is a multivalentisocyanate-type crosslinking agent or a multivalent epoxy-typecrosslinking agent, which has 3 or more functional groups in a molecule.

A crosslinking degree can be appropriately selected depending on a usepurpose. When a copolymerizing crosslinking agent is used, an amount ofthe crosslinking agent is preferably 0.001 to 10% by weight, morepreferably 0.01 to 5% by weight relative to a total monomer weight.

When a reactive crosslinking agent is used, a preferable addition amountis different depending on a kind of a product to be made utilizing thecrosslinked body of the present invention and, when a non-aqueousabsorbent sheet or a non-aqueous absorbent agent described later ismade, an amount is preferably 0.001 to 10% by weight based on a totalpolymer weight. When an integrated gel containing an organic solventdescribed later is made, an amount is preferably 0.01 to 50% by weight.

In the present invention, a method of polymerizing the carboxyl groupand/or sulfonate group-containing monomer, the monomer substituted withan onium cation, and other monomer (b′) to be copolymerized if necessarymay be the known method, and examples include a solution polymerizationmethod in which polymerization is performed in a solvent capable ofdissolving the aforementioned respective monomers and the producedpolymer, a bulk polymerization method of performing polymerizationwithout using a solvent, an emulsion polymerization method and the like.Among them, preferable is a solution polymerization method.

An organic solvent in solution polymerization can be appropriatelyselected depending on a solubility of a monomer and a polymer used, andexamples include alcohols such as methanol, ethanol and the like,carbonates such as ethylene carbonate, propylene carbonate, dimethylenecarbonate and the like, lactones such as γ-butyrolactone and the like,lactams such as ε-caprolactam and the like, ketones such as acetone,methyl ethyl ketone and the like, carboxylic acid esters such as ethylacetate and the like, ethers such as tetrahydrofuran, dimethoxyethaneand the like, aromatic hydrocarbons such as toluene, xylene and thelike, and water. These solvents may be used alone, or by mixing two ormore.

The polymerization concentration in solution polymerization is notparticularly limited, and is different variously depending on a usepurpose, but is preferably 1 to 80% by weight, more preferably 5 to 60%by weight.

A polymerization initiator may be a normal initiator, and examplesinclude azo-based initiators [azobisisobutylonitrile, azobiscyanovalericacid, azobis(2,4-dimethyl)valeronitrile],azobis(2-amidinopropane)dihydrochloride,azobis{2-methyl-N-(2-hydroxyethyl)propionamide} etc.), peroxide-basedinitiators [benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide,succinic acid peroxide, di(2-ethoxyethyl)peroxy dicarbonate, hydrogenperoxide etc.], and redox initiators [combination of the aforementionedperoxide-based initiator and a reducing agent (ascorbic acid orpersulfate salt) etc.].

Examples of other polymerization method include a method of adding aphotosensitive initiator [benzophenone etc.] and irradiatingultraviolet-ray, and a method of performing polymerization byirradiating radiation such as γ-ray and electron beam.

An amount of an initiator to be added when a polymerization initiator isused is not particularly limited, but is preferably 0.0001 to 5% byweight, more preferably 0.001 to 2% by weight relative to a total weightof monomers used.

A polymerization temperature is different variously depending on adesired molecular weight, a degradation temperature of an initiator, anda boiling point of a solvent used, and is preferably −20 to 200° C.,more preferably 0 to 100° C.

The non-aqueous absorbent (B) of the present invention comprises thethus obtained crosslinked body (A), and can be processed into variousforms depending on a purpose, being not limiting. Examples of apreferable form include particulate and sheet-like forms.

A method of making a preferable form will be explained below, but sincea making method and a preferable method are slightly different dependingon a form, each of them will be explained.

(Form)

When the non-aqueous absorbent (B) comprising the crosslinked body (A)of the present invention is formulated into particulate, a particlediameter as an average particle diameter is preferably 1 to 5,000 μm,more preferably 50 to 2,000 μm.

A method of obtaining a particulate form is not particularly limited aslong as a particulate form is obtained finally, but examples include thefollowing (i) to (iv) methods.

(i) A method of copolymerizing the aforementioned copolymerizingcrosslinking agent using, if necessary, a solvent to prepare anon-aqueous absorbent (B) comprising a crosslinked polymer (1) (A) and,if necessary, distilling off a solvent by a method such as drying, andgrinding using the known grinding method to obtain a particulate form.

(ii) A method of performing polymerization to prepare a polymer (1), andif necessary, using a solvent, crosslinking the polymer (1) by means ofthe aforementioned reactive crosslinking agent or irradiation and thelike, and if necessary, distilling off a solvent by a method such asdrying or the like, and grinding this using the known grinding method toobtain a particulate form.

(iii) A method of copolymerizing the aforementioned carboxyl groupand/or sulfonate group-containing monomer (a′), and if necessary, othermonomer (b′) in the presence of the aforementioned copolymerizingcrosslinking agent, if necessary, using a solvent to obtain acrosslinkied polymer, adding the aforementioned onium cation compound tosubstitute protons of an acid group with a predetermined amount of oniumcations, and if necessary, distilling off a solvent by a method such asdrying or the like, and grinding this using the known grinding method toobtain a particulate form.

(iv) A method of copolymerizing the aforementioned carboxyl group and/orsulfonate group-containing monomer (a′), and if necessary other monomer(b′) in the presence of the aforementioned copolymerizing crosslinkingagent, if necessary, using a solvent without crosslinking to obtain apolymer, crosslinking the polymer with the aforementioned onium cationcompound and reactive crosslinking agent or irradiation at the same timewith substituting protons of an acid group, and if necessary, distillingoff a solvent by a method such as drying or the like, and grinding thisusing the known grinding method to obtain a particulate form.

Drying which is performed, if necessary, during a process of renderingparticulate a shape of a non-aqueous absorbent (B) comprising theaforementioned crosslinked body (A) may be the known drying method, andexamples include ventilation drying (circulating wing drier etc.), gaspermeating drying (band-type drier etc.), vacuum drying (vacuum drieretc.), contact drying (drum drier etc.) and the like.

A drying temperature when drying is performed is not particularlylimited as long as deterioration of a polymer or excessive crosslinkingdoes not occur, but is preferably 0 to 200° C., more preferably 50 to150° C.

A grinding method when a shape is rendered particulate may be the knownmethod and, examples include methods such as impact grinding (high speedrotating-type grinder such as pinmill, cutter mill, ball mill-typegrinder and ACM pulverizer), air grinding (jet grinder etc.), andfreezing grinding.

The non-aqueous absorbent (B) comprising the thus particulatedcrosslinked body (A) has capability of absorbing an organic solvent, andcan be utilized as a non-aqueous absorbent agent (E).

A liquid holding amount of the non-aqueous absorbent (B) of the presentinvention varies variously depending on a kind of a subject organicsolvent, a composition of the polymer, a gel strength, and the like.When the (B) is used as a non-aqueous absorbent agent (E), a liquidholding amount for an organic solvent selected from propylene carbonate,γ-butyrolactone, ethanol and methanol is designed at preferably 10 to1,000 g/g, more preferably 50 to 900 g/g. When a liquid holding amountis 10 g/g or larger, a liquid holding amount is considerably larger ascompared with previous non-ionic absorbent, and when a liquid holdingamount is 1,000 g/g or smaller, there is not a problem that a gelstrength of an absorbent agent holding an organic solvent is too weak.

Another invention of the present invention is a non-aqueous gel (C)comprising the aforementioned non-aqueous absorbent (B) and an organicsolvent (2).

A ratio of the non-aqueous absorbent (B)/organic solvent in thisnon-aqueous gel (C) is preferably 0.1 to 99/1 to 99.9% by weight, morepreferably 0.5 to 50/50 to 99.5% by weight, further preferably 1 to30/70 to 99% by weight, most preferably 1 to 20/80 to 99% by weight.When a ratio of the (B) is 0.1% by weight or larger, a gel strength ofthe produced non-aqueous gel (C) is not weak, and a whole can besufficiently gelated. When the ratio is 99.9% by weight or smaller, evenif it is used for gelation of an electrolyte solution, an electricalconductivity of a gel is not reduced, and an amount of a necessaryelectrolyte solution or an electrolyte described later to be added isnot too smaller, not leading to insufficient volume.

Examples of the organic solvent (2) used in the non-aqueous gel (C) ofthe present invention include the same organic solvents as thosedescribed above, and specific examples include alcohol organic solventssuch as methanol, ethanol, propanol, butanol and the like, glycolorganic solvents such as ethylene glycol, propylene glycol and the like,carbonate organic solvents such as dimethyl carbonate, ethylenecarbonate, propylene carbonate and the like, ketone organic solventssuch as acetone, dimethyl ketone, methyl ethyl ketone and the like,ether organic solvents such as diethyl ether, diethoxyethane,tetrahydrofuran, dioxane and the like, aliphatic hydrocarbon organicsolvents such as hexane, octane and the like, aromatic hydrocarbonorganic solvents such as toluene, xylene and the like, carboxylic acidester organic solvents such as methyl acetate, ethyl acetate, propylacetate and the like, lactone organic solvents such as γ-butyrolactoneand the like, and lactam organic solvents such as ε-caprolactam and thelike.

Among them, preferably organic solvents are propylene carbonate,ethylene carbonate, dimethyl carbonate, and dimethoxyethane which are asolvent for lithium batteries; γ-butyrolactone, and ε-caprolactum whichare a solvent for a condenser; methanol, ethanol, and propanol which area solvent for solid fuels or ignition agents; other toluene, xylene,propylene glycol and the like, and a mixture of two or more of them.

In the present invention, these organic solvents may be a solvent inwhich a salt of lithium as an electrolyte used in such as lithiumbatteries contained in the aforementioned organic solvent.

Examples of a kind of a preferable lithium salt contained in theaforementioned organic solvents include one or more kinds of LiClO₄,LiBF₄, LiPH₆, LiAsF₆, LiCF₃SO₃, and Li(CF₈SO₂)₂, and a more preferablesalt is L₁BF₄ and/or LiPH₆.

A content of a lithium salt to be added as necessary can be selectedvariously depending on a purpose or necessity thereof, Li solubility andthe like, and the salt is contained in the aforementioned organicsolvent at preferably 0.5 to 50% by weight, more preferably 1 to 20% byweight.

In the present invention, since an organic solvent containing thelithium salt is used, and there is a possibility that a proton of thecarboxyl group and/or sulfonate group reacts with a lithium salt, asubstitution degree of a proton with an onium cation in this case ispreferably 90 to 100% by mol, more preferably 98 to 100% by mol.

Examples of a method of preparing the non-aqueous gel (C) of the presentinvention include the following (v) to (viii), but it is preferable toprepare an integrated gel by methods exemplified in (vii) and (viii).

(v) A method of adding a predetermined amount of the organic solvent (2)to the aforementioned particualte non-aqueous absorbent (B) of thepresent invention;

(vi) A method of adding the organic solvent (2) to a sheet containingthe non-aqueous absorbent (B);

(vii) A method of dissolving the polymer (1) in the organic solvent (2),and crosslinking the polymer (1) by any crosslinking means ofcrosslinking with the aforementioned linking agent, crosslinking byirradiation with ultraviolet-ray or radiation (electron beam, γ-rayetc.), and crosslinking by heating to obtain an integrated gel;

(viii) A method of obtaining an integrated gel by polymerizing 20 to100% by weight of a carboxyl group and/or sulfonate group-containingmonomer in which from 30 to 100% by mol of protons are substituted withthe aforementioned onium cations, and if necessary, 0 to 80% by weightof other copolymerizable monomer in the organic solvent (2) in thepresence of the aforementioned copolymerizing crosslinking agent.

A form of a gel comprising the non-aqueous absorbent (B) and the organicsolvent (2) can be appropriately selected depending on a purpose and autility. Examples of a shape include sheet-like, block-like, sphericaland cylindrical shapes. Among them, a preferable shape is sheet-like orblock-like and, in particular, when used in a gel battery for mobilephones or computers, sheet-like is preferable.

A thickness of a gel when formulated into a sheet-like gel is preferably1 to 10,000 μm, more preferably 10 to 1,000 μm. A width and a length ofa sheet-like gel may be appropriately selected depending on a usepurpose, a use place, a utility and the like.

A method of preparing gels having these shapes is not particularlylimited, but examples include a method of performing gelating in acontainer or a cell in conformity with a shape which is wanted to beprepared, and a method of preparing a sheet-gel by laminating or coatinga mixture of the polymer (1), the monomer or the like and the organicsolvent (2) on a releasing paper, a film, a non-woven fabric or thelike.

Since the non-aqueous absorbent (B) or the non-aqueous absorbent agent(E) and/or the non-aqueous gel (C) of the present invention can gelate alarge amount of an organic solvent for lithium batteries at a smallamount of them, increase in a ratio of an electrolyte solution becomespossible, and as a result, since increase in ionic conductivity becomespossible, they can be suitably used as a gelating agent for lithiumbatteries.

Then, the case where the non-aqueous absorbent (B) of the presentinvention is shaped into a sheet will be explained.

The non-aqueous absorbent sheet (D) of the present invention comprisesthe aforementioned non-aqueous absorbent (B), and a substrate selectedfrom the group consisting of a non-woven fabric, a woven fabric, a paperand a film.

Examples of a method of obtaining a sheet-like shape include thefollowing (ix) to (xi) methods.

(ix) A method of holding the aforementioned particulate non-aqueousabsorbent (B) between non-woven fabrics or papers to obtain a sandwichsheet.

(x) A method of impregnating and/or coating one or more substratesselected from the group consisting of a non-woven fabric, a wovenfabric, a paper and a film with the uncrosslinked polymer (1), and then,crosslinking the polymer (1) using one or more crosslinking meansselected from the group consisting of crosslinking with theaforementioned crosslinking agent, crosslinking by irradiation withultraviolet-ray or radiation (electron beam, Tray etc.), andcrosslinking by heating, and at the same time, if necessary, distillingoff a solvent to obtain a sheet.

(xi) A method of impregnating and/or coating one or more substratesselected from the group consisting of a non-woven fabric, a wovenfabric, a paper and a film with a mixed solution containing 20 to 100%by weight of a carboxyl group and/or a sulfonate group-containingmonomer in which from 30 to 100% by mol of protons are substituted withthe aforementioned onium cations, 0 to 80% by weight of othercopolymerizable monomer and the aforementioned crosslinking agent, andthen, polymerizing the substrate using one or more crosslinking meansselected from the group consisting of crosslinking by a polymerizationinitiator and/or irradiation with ultraviolet-ray or radiation (electronbeam, γ-ray etc.), and crosslinking by heating and, if necessary,distilling off a solvent to obtain a sheet.

Among these methods, it is preferable to use a method of (x) or (xi)from a viewpoint of easy adjustment of a thickness of a sheet and anabsorbing rate.

A thickness when a shape is a sheet is preferably 1 to 5,000 μm, morepreferably 5 to 2,000 μm, further preferably 10 to 1,000 μm. When athickness of a sheet is 1 μm or larger, a basis amount of thenon-aqueous absorbent (B) becomes insufficient and, when the thicknessis 5,000 μm or smaller, a thickness of the sheet is sufficient.

A length and a width of a sheet are not particularly limited, and can beappropriately selected depending on a use purpose and a utility, but apreferable length is 0.01 to 10,000 m, and a preferable width is 0.1 to300 cm.

A basis weight of the non-aqueous absorbent (B) of the present inventionin the sheet is not particularly limited, but when capabilities ofabsorbing and holding a subject organic solvent, and not too largethickness are considered, a basis weight is preferably 10 to 3,000 g/m²,more preferably 20 to 10,000 g/m².

In the present invention, a substrate such as a non-woven fabric, awoven fabric, a paper, a film and the like to be used if necessary torender a shape sheet-like may be the known-substrate, and examplesinclude a non-woven fabric or a woven fabric composed of a syntheticfiber and/or a natural fiber having a basis weight of around 10 to 500g/m², a paper (wood free paper, thin paper, Japanese paper etc.), a filmcomposed of a synthetic resin, and a substrate of two or more of them,and a composite of them.

Among these substrate, preferable is a non-woven film, and a compositeof a non-woven fabric and a film, and more preferably is a compositecomposed of a film having one side of a non-woven fabric and one sidehaving no liquid-permeating property.

In the present invention, a thickness of these substrates is preferably1 to 5,000 μm, more preferably 10 to 2,000 μm. When a thickness is 1 μmor larger, impregnation or coating with a predetermined amount of thepolymer (1) becomes easy. On the other hand, when a thickness is 5,000μm or smaller, a sheet is not too thick, and a sheet is easily used.

A method of coating or impregnating a substrate with the polymer (1) maybe the known method. For example, normal methods such as coating andpadding may be applied. After coating or padding treatment, a solventused for polymerization, dilution or viscosity adjustment may be, ifnecessary, distilled off by a method such as drying or the like.

Since the thus prepared sheet containing the non-aqueous absorbent (B)of the present invention effectively absorbs an organic solvent, thesheet is used as a non-aqueous absorbent sheet (D), and is mainly usedas a non-aqueous absorbent sheet or a leakage-preventing sheet fororganic solvents or organic solvent electrolyte solutions in lithiumprimary batteries, secondary batteries, and condensers.

An absorbing amount of this non-aqueous absorbent sheet (D) is variouslydifferent depending on a use purpose, but a liquid-holding amount(absorbing amount after centrifugation dehydration) for propylenecarbonate which is a representative solvent of a lithium battery ispreferably 0.1 to 100 g/cm², preferably 1 to 100 g/cm². When aliquid-holding amount is 0.1 g/cm² or larger, an electrolyte solutioncan be sufficiently held, and when the amount is 100 g/cm² or smaller, asheet which has absorbed an organic solvent does not become too thick.

In the present invention, the non-aqueous absorbent (B) can be used as agel electrolyte for lithium batteries, but from a viewpoint of contactwith an electro rode (interface), a sheet-like crosslinked body (A)which has absorbed an organic solvent containing the aforementionedlithium electrolyte, or an integrated non-aqueous gel (C) comprising thenon-aqueous absorbent (B) and an organic solvent containing theaforementioned lithium electrolyte may be used as a gel electrolyte.

EXAMPLES OF UTILITIES

From the foregoing, under the aforementioned various forms, thenon-aqueous absorbent (B) of the present invention is useful in a widerange of utilities such as a leakage-preventing sheet and a liquid stopagent for electronic and electric appliances and automobile organicsolvent batteries, condensers, capacitors and the like, an ignitionagent, organic solvent batteries and gel electrolyte batteries ofcondensers, alcohol-based bactericidal materials or alcohol-basedbactericides, cold insulating materials or cold insulators, gel sheetsfor cooling, fuel compositions for solid fuels or solid fuels using thesame, fragrance materials or fragrances, patch materials or patches,insecticidal compositions or insecticides, or fuel stores for fuelbatteries or fuel batteries using the same. In addition, in particular,the non-aqueous absorbent sheet (D) is useful in electrolyte solutionsof lithium primary batteries, lithium secondary batteries or condensers.

Among the aforementioned utility examples, alcohol-based bactericidalmaterials or alcohol-based bactericides, cold insulating materials orcold insulators, gel sheets for cooling, fuel compositions for solidfuels or solid fuels using the same, fragrance materials and coldinsulators, patch materials or patches, insecticidal compositions orinsecticides, or fuel stores for fuel batteries or fuel batteries usingthe same will be described in detail below.

[Alcohol-Based Bactericidal Materials and Alcohol-Based Bactericides]

An alcohol-based bactericidal material comprising the non-aqueousabsorbent (B) and an alcohol solvent, can be processed into variousforms depending on a purpose. Examples of a preferable form include theaforementioned particulate, sheet-like, and integrated gelated forms,being not particularly limited. In the present invention, an alcoholsolvent refers to a water-soluble alcohol alone which can be mixed withwater at an arbitrary ratio, or a mixture of this and water. Preferableexamples include a mixture of one or more alcohols selected from thegroup consisting of methanol, ethanol and isopropyl alcohol(hereinafter, abbreviated as IPA) and water, being not particularlylimited. Particularly preferable is a mixture of ethanol and water.

An amount of absorbing an alcohol solvent of an alcohol-basedbactericidal material is such that an amount of absorbing ethanol and/ormethanol is designed at preferably 10 to 1,000 g/g, more preferably 50to 900 g/g. When an absorbing amount is 10 g/g or larger, aliquid-holding amount is considerably larger as compared with theprevious non-ionic absorbent. When the amount is 1,000 g/g or smaller,there is not a problem that a gel strength of an alcohol-basedbactericidal material holding an alcohol solvent is too weak.

When a shape of an alcohol-based bactericidal material is formulatedinto a sheet, a shape is as described for the aforementioned non-aqueousabsorbent (B) shaped into a sheet. That is, a thickness, a length and awidth of a sheet; a substrate to be used, and a basis weight are asdescribed above. However, among substrates, preferable are a non-wovenfabric, and a composite of a non-woven fabric, a plastic film and ametal film, and more preferable is a composite having one surfacecomposed of a non-woven fabric, and another surface composed of aplastic film and a metal film having no liquid permeability. Inaddition, a thickness of a substrate, a method of coating orimpregnating a substrate with the polymer (1), and the like are asdescribed above. Since the thus prepared alcohol-based bactericidalmaterial contains the sheet-like non-aqueous absorbent (B) of thepresent invention, and effectively absorbs an alcohol solvent, thematerial is suitably used as a sheet-type alcohol-based bactericidalmaterial.

Another aspect is an integrated gelated-type alcohol-based bactericidalmaterial comprising the aforementioned non-aqueous absorbent (B) and analcohol solvent.

As a method of preparing the integrated gelated-type alcohol-basedbactericidal material, for example, (v) a method of adding apredetermined amount of an alcohol solvent to the aforementionedparticulate non-aqueous absorbent (B); (vi) a method of adding analcohol solvent to a sheet containing the non-aqueous absorbent (B) maybe used, and these alcohol-containing gels are preferably such that anintegrated gel is prepared by the methods exemplified in (vii) and(viii).

A ratio of the non-aqueous absorbent (B)/alcohol solvent in thisintegrated gelated-type alcohol-based bactericidal material ispreferably 0.1 to 99/1 to 99.9% by weight, more preferably 0.5 to 50/50to 99.5% by weight, more preferably 1 to 30/70 to 99% by weight, mostpreferably 1 to 20/80 to 99% by weight. When a ratio of the non-aqueousabsorbent (B) is 0.1% by weight or larger, a gel strength of theproduced alcohol-containing gel is not weak, and a whole can not begelated in any cases. On the other hand, the content is 99% by weight orsmaller, the gel can be sufficiently used as an integrated gelated-typealcohol-based bactericidal material.

A form of the integrated gel comprising the non-aqueous absorbent (B) ofthe present invention and an alcohol solvent can be appropriatelyselected depending on a purpose and a utility, and examples of a shapeinclude sheet-like, block-like, spherical, and cylindrical shapes. Amongthem, a preferable shape is sheet-like or block-like shape. When used asan alcohol-based bactericidal material for storing foods, a sheet-likeshape is preferable. When formulated into a sheet-like gel, a thicknessof gel is a preferably 1 to 10,000 μm, more preferably 10 to 1,000 μm. Awidth and a length of a sheet-gel may be appropriately selecteddepending on a use purpose, a use place, a utility and the like.

A method of preparing a gel having these shapes is not particularlylimited, but examples include a method of performing gelating in acontainer or a cell in conformity with a shape which is wanted to beprepared, and a method of preparing a sheet-like gel by laminating orcoating a mixture of the polymer (1), the monomer or the like and analcohol solvent on a releasing paper, a film, a non-woven fabric or thelike.

In addition, in order to contact feeling, if necessary, a water-solublepolymer such as polyvinyl alcohol, sodium polyacrylate, polyacrylamideand the like, a water-absorbing polymer such as crosslinked-polyacrylatesalt, starch acrylate graft and the like, and a natural thickener suchas pullulan, carrageenan and the like may be added to an alcohol-basedbactericidal material.

In addition, another invention is an alcohol-based bactericide in whichthe alcohol-based bactericidal material is accommodated in an externalmaterial, at least a part of which is composed of a substrate throughwhich a steam of an alcohol solvent, preferably, a steam of ethanol canpermeate (hereinafter, referred to as steam permeable substrate).

Herein, the aforementioned alcohol solvent steam permeable substrate isa substrate having an alcohol solvent steam permeability, preferably, anethanol steam permeability of 0.1 g/m²-24 hr (50% RH/40° C.) or larger,more preferably 1 g/m²-24 hr (50% RH/40° C.) or larger, furtherpreferably 5 g/m²-24 hr (50% RH/40° C.) or larger. Herein, an alcoholsolvent steam permeability is expressed by an amount (g) of an alcoholsolvent steam which passes through 1 m² of a substrate under environmentof a temperature of 40° C. and a relative humidity of 50% for 24 hours,and a value thereof is measured according to JIS-Z-0208 generally usedfor measuring a water steam permeation amount of a resin film. As amaterial used as such the substrate, a sheet having pores or voids suchas a paper, a non-woven fabric, a perforated plastic film, a microporousmembrane and the like, a poreless film such as polyethylene,polypropylene, ethylene-vinyl acetate copolymer (EVA), ethylene-vinylalcohol copolymer (EVAL), polyvinyl alcohol, ionomer, nylon, cellulosetriacetate and the like, or a laminate thereof are used. Any materialsmay be used as long as contents thereof are riot leaked. If necessary,substrates may be subjected to water resistance treatment, oilresistance treatment, or printing.

Alternatively, a part of a substrate may be alcohol solvent steamimpermeable. In this case, any sheets may be used as long as contentsthereof are not leaked, and a material there of is not particularlylimited.

In this alcohol-based bactericide, materials other than the non-aqueousabsorbent (B) and the alcohol solvent may be present in the externalmaterial. Examples include a resin which absorbs the alcohol solvent, anethanol carrier such as silicon dioxide, vermiculite and the like, anoxygen scavenger comprising an iron powder and an oxidation promotersuch as sodium chloride, an aldehyde absorber such as polyallylamine andanionic exchange resin, ethylene adsorbent, ethylene generator, perfumeand the like, other than the aforementioned non-aqueous absorbent (B),being not limiting. A method of allowing the aforementioned oxygenscavenger, aldehyde adsorbent, ethylene adsorbent, ethylene generator,perfume and the like to be present together is not particularly limitedas long as sterilizing disinfecting effect of an alcohol-basedbactericidal material and effects of other materials present therein arenot prevented. For example, these materials may be mixed with analcohol-based bactericidal material composition in advance, andaccommodated into the external material to prepare a laminate sheethaving a structure of (external material/the aforementioned non-aqueousabsorbent (B)+coexisting substance/external material). Alternatively,these coexisting materials may be accommodated in a layer different froma layer in which the non-aqueous absorbent (B) is accommodated. In thiscase, by allowing to a sheet to intervene between the non-aqueousabsorbent (B) layer and a coexisting material layer, a laminate sheethaving a structure of (external material/the aforementioned non-aqueousabsorbent (B) layer/intervening sheet/coexisting material layer/externalmaterial) may be prepared.

Since the non-aqueous absorbent (B) in the alcohol-based bactericide ofthe present invention can gelate a large amount of an alcohol solvent ata small amount, it becomes possible to hold a large amount of an alcoholsolvent, and disinfecting or sterilizing effect lasts for a long periodof time. Therefore, this can be suitably used as an alcohol-basedbactericide such as a sheet-type alcohol-based bactericide, anintegrated gelated-type alcohol-based bactericide and the like.

In addition, an alcohol-based bactericide in which the alcohol-basedbactericidal material is accommodated in an external material, at leasta part of which comprises a substitute through which a steam of analcohol solvent can permeate, has no fear of pollution due to leakage ofthe contents. Alternatively, by accommodation in an external materialhaving an regulated steam permeation amount, since disinfecting orsterilizing effect lasts for a longer time, the bactericide is used fortreating foods by accommodating this and foods in a container havingalcohol solvent steam retainability. Inter alia, the bactericide can beparticularly suitably used for retaining freshness of breads,confectionary, processed foods, dry foods, cereals and the like.

[Cold Insulating Materials and Cold Insulators]

The cold insulating material of the present invention comprises thenon-aqueous absorbent (B) and an alcohol solvent, and an alcohol solventto be used may be the same as that used in the aforementionedalcohol-based bactericidal material.

An amount of absorbing an alcohol of the cold insulating material has noproblem when the amount is designed as in the aforementionedalcohol-bactericidal material. When a sheet of the cold insulatingmaterial is sheet-like, a shape may be sheet-like as in the case of thealcohol-based bactericidal material. A substrate such as a non-wovenfabric, a woven fabric, a paper, a film and the like which are, ifnecessary, used in order to render a form sheet-like may be the knownsubstrate. Examples include a non-woven fabric or a woven fabriccomprising a synthetic fiber and/or a natural fiber having a basisweight of around 10 to 500 g, a paper (wood free paper, thin paper,Japanese paper etc.), a film comprising a synthetic resin, a substrateof two or more of them, and a composite thereof. Among these substrates,preferable are a non-woven fabric, and a composite of a non-woven fabricand a film, and particularly preferable is a composite having onesurface composed of a non-woven fabric and one surface composed of afilm having no liquid permeability. A thickness, a length and a width ofa sheet are as described for the aforementioned alcohol-basedbactericidal material. A thickness of a substrate, and a method ofcoating or impregnating a substrate with a polymer (1) may be the sameas those of the aforementioned alcohol-based bactericidal material. Thethus prepared cold insulating material has a sheet-like form containingthe non-aqueous absorbent (B) of the present invention, and effectivelyabsorbs an alcohol solvent. Therefore, since the material retainssoftness even at freezing, and has cold insulating effect sustained fora long time, the material can be suitably used as a cold insulator.

Another aspect is an integrated gelated-type cold insulating materialcomprising the aforementioned non-aqueous absorbent (B) and an alcoholsolvent. A ratio of the non-aqueous absorbent (B)/alcohol solvent inthis integrated gelated-type cold insulating material, and a method ofpreparing the material may be the same as those of the aforementionedintegrated gelated-type alcohol-based bactericidal material.

Thereupon, a form of a gel comprising the non-aqueous absorbent (B) andan alcohol solvent, and a method for preparing the gel may be the sameas those of the aforementioned alcohol-based bactericidal material. Inorder to improve contact feeling, the same materials as those of theaforementioned alcohol-based bactericidal material may be added to thecold insulating material. By further adding a freezing-point depressantto an alcohol solvent, a freezing point may be further lowered, and itbecomes possible to maintain softness at a lower temperature. Examplesof such the freezing-point depressant include organic materials such aspolyhydric alcohol (sorbitol etc.), urea and the like, and inorganicsalts such as sodium chloride, lithium chloride, magnesium chloride,ammonium nitrate and the like. The freezing-point depressant is notparticularly limited as long as it is a material which has afreezing-point lowering ability, and is dissolved in an alcohol solventPreferable are inorganic salts. An amount of a freezing-point depressantto be added to an alcohol solvent is not particularly limited as long asthe depressant is dissolved in an alcohol solvent, and freezing pointlowering ability is exerted. Alternatively, in order to further increasecooling feeling, menthol may be incorporated. In addition, in order toprevent erroneous drinking, as a bitter ingredient, urea, phenylurea,caffein, naringin, nicotine, tenulin, lactucin, marrubiin, amarogentin,swelcide, aucubin, loganin, colchline, casterin, jasminine, denatoniumbenzoate and the like may be incorporated.

In addition, another invention is a cold insulator in which theaforementioned cold insulating material is accommodated in an externalmaterial comprising a substrate not allowing a steam of an alcoholsolvent, preferably, a steam of ethanol to permeate (hereinafter, steamimpermeable substrate), in order to suppress evaporation of an alcohol.

Herein, an alcohol solvent steam impermeable substrate is a substratehaving an alcohol solvent steam permeability, for example, an ethanolsteam permeability of preferably 10 g/m²·24 hr (50% RH/40° C.) orsmaller, more preferably 1 g/m² 24 hr (50% RH/40° C.) or smaller,further preferably 0.1 g/m²·24 hr (50% RH/40° C.) or smaller. Herein, analcohol solvent steam permeability is expressed by an amount (g) of analcohol solvent steam passing through 1 m² of a substrate underenvironment of a temperature of 40° C. and a relative humidity of 50%for 24 hours, and a value thereof is measured according to JIS-Z-0208generally used for measuring a steam permeation amount of a resin film.Examples of a material used as such the substrate include a plastic filmsuch as low density polyethylene, biaxial-stretched polypropylene,polyester, nylon, polyvinyl chloride, polyvinylidene chloride and thelike, and a laminate thereof, a metal film such as an aluminum foil, analuminum-deposited film and the like, and the laminate thereof, alaminate of the plastic film and the metal film, and a laminate of thosematerials and a paper, a non-woven fabric, a woven-fabric and the like.A substrate which has alcohol steam impermeability and in which contentsthereof are not leaked therefrom, is preferable, being not limiting.

In the cold insulator of the present invention, materials other than theaforementioned non-aqueous absorbent (B) and the aforementioned alcoholsolvent may be present together in the aforementioned external material.Such the material and laminated sheet are as described for theaforementioned alcohol-based bactericidal material.

[Gel Sheets for Cooling]

The gel sheet for cooling of the present invention is formed of a gellayer of the aforementioned cold insulating material and a support. Thegel layer can be processed into various forms depending on a purpose,being not particularly limiting. Examples of a preferable form includeparticulate, sheet-like, and integrated gelated-type forms. Morepreferable is sheet-like. A method of preparing a sheet-like gel layeris as described for preparation of the sheet-like cold insulatingmaterial. A thickness and a length of a sheet, an additive, a kind and athickness of a substrate, a coating method, absorbing ability and thelike are preferably the same as those of the cooling insulatingmaterial.

Examples of a support is not particularly limited, but specifically,examples include a combination of one or more selected from the groupconsisting of a steam permeable substrate having an alcohol solventsteam permeability exceeding 0.1 g/m²·24 hr (50% RH·40° C.) as in theaforementioned alcohol-based bactericidal material, an external materialand a pressure-sensitive adhesive layer.

A pressure-sensitive adhesive agent constituting the pressure-sensitivelayer may be the known pressure-sensitive adhesive used in a cataplasmor the previous gel sheet for cooling, and examples include apressure-sensitive adhesive such as thermally crosslinked CMC, gelatin,gum arabic and the like. Among them, preferable are thermallycrosslinked CMC, gelatin and the like which have high safety even whencontacted with a skin.

Among these supports, preferable is the aforementioned steam permeablesubstrate, and further preferable is a non-woven fabric.

In the gel sheet for cooling, a support is contacted with at least apart of a gel layer. An area with which a support is contacted is notparticularly limited as long as a part of a gel layer is exposed, butpreferably 75% or smaller, more preferably 65% or smaller, furtherpreferably 50% or smaller of a surface area of a gel layer. Therefore,as a preferable aspect of a gel sheet for cooling, a gel layer isattached to one surface of the aforementioned steam permeable substrate.A pressure-sensitive adhesive may be directly contacted with a gellayer.

A size of a gel sheet for cooling of the present invention can bearbitrarily adjusted depending on a use purpose.

For example, when used on a forehead of a head, around 5 cm×10 cm ispreferable. In the case of back of a foot, 5 to 6 cm×20 to 25 cm ispreferable. A size of the sheet may be adjusted to these sizes at eitherof preparation or use.

In another preferable aspect, a gel layer is accommodated in an externalmaterial. That is, in order that an alcohol solvent is not evaporateduntil a gel sheet for cooling is used, it is preferable that a gel layerpart is covered and sealed with a substrate having an alcohol solventsteam permeability of 0.1 g/m²·24 hr (50% RH/40° C.) or smaller, and agel layer part is opened upon use to evaporate an alcohol solvent.Examples of this substrate having an alcohol solvent steam permeabilityof 0.1 g/m²·24 hr (50% RH/40° C.) or smaller include a paper having lowsteam permeability (e.g. oiled paper etc.), a non-woven fabric (e.gresin-processed fabric), a plastic film (poreless film such aspolyethylene, polypropylene, ethylene-vinyl acetate copolymer (EVA),ethylene-vinyl alcohol copolymer (EVAL), polyvinyl alcohol, ionomer,nylon, cellulose triacetate etc.) and the like.

Alternatively, in the aforementioned construction, a pressure-sensitiveadhesive may be combined with an external material. An area on which apressure-sensitive adhesive is attached to an external material ispreferably 50% or smaller, more preferably 25% or smaller of a surfacearea of the aforementioned gel layer.

When a pressure-sensitive adhesive is used, the gel sheet for coolingcan be easily fixed to a human body by adhering to a skin, and a gellayer having elasticity accommodated in an outer material exerts coolingeffect as a cooling agent for a long time.

Since the non-aqueous absorbent (B) in a gel layer in the presentinvention can gelate a large amount of alcohol solvent at a smallamount, it becomes possible to retain a large amount of an alcoholsolvent, and softness is retained even at freezing, and cooling effectlasts over a long time. Therefore, this can be suitably used as a gelsheet for cooling.

In addition, when the gel sheet for cooling of the present invention isaccommodated in an outer material, at least a part of which comprises asubstrate through which an alcohol solvent steam can permeate, there isno fear of pollution due to leakage of the contents, and since coolingeffect lasts over a longer time by accommodating in an outer materialhaving a regulated steam permeation amount, this is suitable as a gelsheet for cooling.

That is, the gel sheet for cooling of the present invention absorbs heatfrom the surrounding due to evaporation latent heat due tovolatilization of an alcohol solvent contained in gel layer from thesurface of a gel layer, and has cooling effect even when a gel sheet forcooling is not especially cooled. By freezing with a freezer, it becomespossible to cool for a further long time.

[Fuel Compositions for Solid Fuels or Solid Fuels Using the Same]

The fuel composition for solid fuels of the present invention is acomposition comprising the non-aqueous absorbent (B) and an alcoholsolvent, and the solid fuel uses the same. As the alcohol solvent usedin the fuel composition for solid fuels and the solid fuel of thepresent invention, an alcohol fuel is used.

Herein, the alcohol fuel refers to an alcohol alone which easilyinitiates combustion when ignited with a lighter, a match or the like,or a mixture of this and a combustible organic solvent which is miscibletherewith. Preferable is an alcohol alone. A preferable alcohol includesmethanol, ethanol, isopropyl alcohol, butanol and a mixture thereof, anda more preferable alcohol includes methanol, ethanol and a mixturethereof.

As used herein, a miscible combustible organic solvent refers to anorganic solvent which can be mixed with the alcohol fuel at an arbitraryratio, and in which a mixture with the alcohol fuel easily initiatescombustion when ignited with a lighter, match or the like. Thecombustible organic solvent is not particularly limited as long as it issuch the solvent, and preferable examples include ketones such asacetone, methyl ethyl ketone and the like, esters such as ethyl acetate,butyl acetate and the like, ethers such as diethyl ether,tetrahydrofuran and the like, and polyhydric alcohols such as ethyleneglycol, propylene glycol and the like.

When the fuel composition for solid fuels is shaped into a sheet, thesheet may be the same as that of the aforementioned alcohol-basedbactericidal material. A thickness, a length and a width of a sheet; asubstrate to be used, and a basis weight may be the same as those of theaforementioned alcohol-based bactericidal material. A thickness of abase, and a method of coating or impregnating a substrate with thepolymer (1) may be the same as those described above. Since the thusprepared fuel composition for solid fuels contains the sheet-likenon-aqueous absorbent (B) of the present invention, and effectivelyabsorbs an alcohol fuel, the composition is suitably used as asheet-type fuel composition.

Another aspect is an integrated gelated-type fuel composition comprisingthe non-aqueous absorbent (B) and an alcohol fuel. A ratio of thenon-aqueous absorbent (B)/alcohol fuel, and a process for preparing acomposition in this integrated gelated-type fuel composition may be thesame as those of the aforementioned integrated gelated-typealcohol-based bactericidal material.

In addition, an amount of absorbing an alcohol fuel in the fuelcomposition for solid fuels may be designed as in the case of thealcohol-based bactericidal material.

A form of a gel comprising the non-aqueous absorbent (B) and an alcoholsolvent, and a method of preparing the same may be as in thealcohol-based bactericidal material. If necessary, one or more selectedfrom the group consisting of other gelating agent (fatty acid soap,dibenzalsorbitol, hydroxypropylcellulose, benzylidenesorbitol,carboxyvinylpolymer, polyethylene glycol, polyoxyalkylene, sorbitol,nitrocellulose, methylcellulose, ethylcellulose, acetylbutylcellulose,polyethylene, polypropylene, polystyrene, ABS resin, AB resin, acrylicresin, acetal resin, polycarbonate, nylon, phenol resin, phenoxy resin,urea resin, alkyd resin, polyester, epoxy resin, diallyl phthalateresin, polyallomer etc.), a thickener, a binder, a carbonaceous solidfuel (charcoal, oval briquet, briquet, anthracite, sawdust charcoal,used charcoal, papers, hemp, cotton, hair, silk, paraffin etc.), anigniting agent, a conbustion accelerator (oxidizing agent such aspermanganates, nitrates, perchlorates etc.), a combustion inhibitor(silicates such as silica gel etc.), clay such as bentonite, kaolinite,montmorillonite etc., potter's clays), a fire sparks flight preventingagent, a compound and/or a complex containing a metal exhibiting a flamereaction (strontium, lithium, calcium, sodium, barium, copper, potassiumetc.), and a perfume (animal perfume such as musk, civet etc., plantperfume such as lemongrass oil, mentha oil etc., synthetic perfume suchas limonene, isobutylaldehyde, menthol, eugenol, camphor, coumarin,benzyl acetate etc.) may be incorporated into the fuel composition forsolid fuels of the present invention. These are not particularly limitedas long as they can exert their function, whether solid or liquid. Inaddition, these may be incorporated at an arbitrary stage of preparationof the fuel composition for solid fuels.

A form of the fuel composition for solid fuels of the present inventionis selected from the group consisting of solid-like, gel-like,pellet-like and sheet-like. The solid fuel of the present invention ischaracterized in that the aforementioned fuel composition for solidfuels is accommodated in an external material comprising a substratethrough which a steam of an alcohol fuel, preferably, a steam of ethanoldoes not permeate (hereinafter, referred to as steam impermeablesubstrate), in order to suppress volatilization of a fuel. In this case,an alcohol solvent (alcohol fuel) steam permeability of the steamimpermeable substrate is as in the case of the aforementionedalcohol-based bactericidal material.

In an external material for the solid fuel, for example, a resin ofabsorbing the alcohol fuel, an ethanol carrier such as silicon dioxide,vermiculite etc., an igniting agent, a combustion accelerator, acombustion inhibitor, a fire sparks flight preventing agent, a compoundand/or a complex containing a metal exhibiting a flame reaction, aperfume, a antiseptic, a mildewproofing agent, an antioxidant, anultraviolet absorbing agent and the like may coexist, in addition to thenon-aqueous absorbent (B), being not limiting. A laminate sheet may beas in the alcohol-based bactericidal material.

Since the non-aqueous absorbent (B) which is a constituent of the fuelcomposition for solid fuels of the present invention can gelate a largeamount of alcohol fuel at a small amount, it becomes possible to retaina large amount of alcohol fuel, and combustion lasts over a long time,the non-aqueous absorbent of the present invention can be suitably usedas a solid fuel.

In addition, since the solid fuel in which the fuel composition forsolid fuels is accommodated in an external material comprising asubstrate through which a steam of an alcohol fuel does not permeate,has no fear of pollution due to leakage of contents, and the decrease ofan amount of holding an alcohol fuel due to volatilization after longterm storage is not occurred, handling and storage become easy, andcombustion lasts for a long time at combustion and, thus, such the solidfuel is suitable as a solid fuel.

[Fragrance Materials or Fragrances]

The fragrance material of the present invention comprises a non-aqueousabsorbent (B) of the present invention and an aromatic drug and it ispreferable that the aromatic drug has normal temperature volatility.

Herein, the aromatic drug having normal temperature volatility is notparticularly limited as long as it has aroma, and is volatilized orevaporated at a normal temperature (normal life temperature, herein, 5to 40° C.), and may be liquid or solid. When the drug is liquid, it canbe used as it is. When the drug is a liquid having a high viscosity andis hardly absorbable, or a solid, the drug can be dissolved in analcohol solvent (ethanol etc.), and then, absorbed in the non-aqueousabsorbent (B) constituting a fragrance material. The concentration atdissolution may be adjusted depending on a use purpose, being notparticularly limited. When the drug is a thermally meltable solid, it isabsorbed in the non-aqueous absorbent (B) constituting a fragrancematerial, after thermal melting. Specifically, there are naturalperfumes and synthetic perfumes.

Examples of the natural perfume include animal perfumes such as musk,civet, ambergris and the like, natural plant oils such as abies oil,almond oil, bazin, birch oil, cajabute oil, cardamon oil, celery oil,cinnamon oil, citronella oil, cognac oil, cumin oil, camphol oil,estogoran oil, eucalyptus oil, garlic oil, ginger oil, grapefruit oil,hop oil, lemon oil, timewhite oil, lemongrass oil, cassia oil, vimentoil, cypress oil, white-sedar leaf oil, floral oil, nutmeg oil, mandarinoil, pepper oil, oragne oil, turpentine oil and the like, and citral,cinnamic aldehyde, thymol, eugenol, rosemary, sage and the like as anatural plant oil extract. Examples of the synthetic perfume includehydrocarbons such as pinene, limonene and the like, alcohols such asgeraniol, citroneol, menthol, borneol, benzyl alcohol and the like,phenols such as eugenol and the like, aldehydes such asisobutylaldehyde, cetral, citronellal, cinnamicaldehyde and the like,ketones such as acetophenone and the like, lactones such as coumarin andthe like, and esters such as benzyl acetate, cinnamyl acetate, isopropylisobutyrate, benzyl benzoate, cinnamyl cinnamate and the like.

These may be used alone, or may be a perfume obtained by compounding twoor more kinds.

An amount of absorbing an aromatic drug of the non-aqueous absorbent (B)constituting the fragrance material may be designed as in an alcoholabsorbing amount in the case of the alcohol-based bactericidal material.

When the fragrance material is shaped into a sheet, the sheet may be asin the case of the aforementioned alcohol-based bactericidal material. Athickness, a length and a width of a sheet; a substrate used, athickness of a substrate, a method of coating or impregnating asubstrate with the non-aqueous absorbent (B), and a basis weight may bethe same as those of the alcohol-based bactericidal material. Since thethus prepared fragrance material contains the sheet-like non-aqueousabsorbent (B) of the present invention, and effectively absorbs anaromatic drug, the material is useful as a sheet-type fragrance.

Another aspect is an integrated gelated-type fragrance materialcomprising the (B) and an alcohol solvent. A ratio of the (B)/aromaticdrug, and a method of preparing a material in this integratedgelated-type fragrance material may be as in the aforementionedalcohol-based bactericidal material.

A form of a gel of the integrated gelated-type fragrance materialcomprising (B) and an aromatic drug, and a method for preparing the samemay be as in the alcohol-based bactericidal material. In order toimprove contact feeling, the same materials as those for theaforementioned alcohol-based bactericidal material may be added to theintegrated gelated-type fragrance material.

In addition, the fragrance of the present invention is characterized inthat the fragrance material is accommodated in an external material, atleast a part of which comprises a substrate through which a steam of anormal temperature volatile component present in the aromatic drug canpermeate. In this case, a normal temperature volatile component steampermeability of a substrate, and a kind of substrate may be as in thealcohol-based bactericidal material.

Materials to be present together in the fragrance material or theexternal material of the fragrance, and the laminated sheet may be as inthe alcohol-based bactericidal material.

In addition, in order to prevent erroneous drinking, urea, phenylurea,caffein, naringin, nicotine, tenulin, lactucin, marrubin, amarogentin,swelcide, aucubin, loganin, colchlone, casterin, jasmine, denatoniumbenzoate and the like as a bitter ingredients may be incorporated in thefragrance of the present invention.

[Patch Materials and Patches]

The patch material of the present invention comprises the non-aqueousabsorbent (B) and a percutaneous absorption drug.

In the present invention, the percutaneous absorption drug is notparticularly limited as long as it has percutaneous absorbability, andmay be liquid or solid. When the drug is liquid, it can be used as itis. When the drug is a liquid having a high viscosity and is hardlyabsorbable, or a solid, the drug may be dissolved in water or an alcoholsolvent (ethanol etc.), and absorbed in the non-aqueous absorbent (B)constituting the patch material. The concentration of the percutaneousabsorption drug at dissolution may be adjusted depending on a usepurpose, being not particularly limited. When the percutaneousabsorption drug is a solid having thermal meltability, it is absorbed inthe non-aqueous absorbent (B) constituting the patch material, afterthermal melting.

In the present invention, specifically, examples of the percutaneousdrug include anti-inflammatory agents such as methyl salicylate, glycolsalicylate, diphenylhydrazines, indometacin, flurbiprofen andketoneprofen, skin stimulating agents such as camphor, menthol and thelike, central nerve acting agents (sleep-analgesic, anti-epilepsy agent,psychoneurotic agent), diuretic, hypotensive agent, coronaryvasodilator, antitussive expectorant, anti-histamine agent, arrhythmiaagent, cardiotonic drug, adrenocortical hormone, anesthetic and thelike. These may be used alone, or by mixing two or more.

An amount of absorbing the perucutaneous absorption drug of the patchmaterial may be designed as in an amount of absorbing an alcohol in thecase of the aforementioned alcohol-based bactericidal material.

When the patch material is shaped into a sheet, the sheet may be as inthe alcohol-based bactericidal material. A thickness, a length and awidth of a sheet; a substrate to be used, a thickness of a substrate, amethod of coating or impregnating a substrate with the non-aqueousabsorbent (B), and a basis weight may be as described above. Since thethus prepared patch material contains the sheet-like non-aqueousabsorbent (B) of the present invention, and effectively absorbs theperucutanous absorption drug, the material is useful as a sheet-typepatch material.

Another aspect is an integrated gelated-type patch material comprisingthe (B) and a percutaneous absorption drug. A ratio of the(B)/percutaneous absorption drug, and a method of preparing the same inthis integrated gelated-type patch material may be as in the integratedgelated-type alcohol-based bactericidal material.

A form of the integrated gelated-type patch material comprising (B) anda percutaneous absorption drug, a method of preparing the same may be asin the alcohol-based bactericidal material.

The patch of the present invention comprises the aforementioned patchmaterial. That is, the patch of the present invention allows theaforementioned patch material to be used. For example, when the patchmaterial is used, it is preferable to combine one or more substratesselected from the group consisting of a non-woven fabric, a wovenfabric, a paper, a plastic film and a metal film. Alternatively, inorder to improve adherability with a skin, a pressure-sensitive adhesivemay be used in the patch of the present invention. Thepressure-sensitive adhesive may be the known pressure-sensitive adhesivewhich is used in the previous patch, and examples includepressure-sensitive adhesives such as sodium polyacrylate, glycerin,sorbitol, gum arabic and the like. Among them, preferable are sodiumpolyacrylate and sorbitol which have high safety even when contactedwith a skin.

In the patch having the aforementioned construction, it is preferablethat a substrate (support) is contacted with at least a part of anintegrated gelated-type patch material (gel layer). An area with which asupport is contacted is not particularly limited as long as a part of agel layer is exposed, and is preferably 75% or smaller, more preferably65% or smaller, further preferably 50% or smaller of a surface area of agel layer. Therefore, a preferable aspect of the patch of the presentinvention is such that a gel layer is attached to one surface of thesupport. Alternatively, a pressure-sensitive adhesive may be directlycontacted with a gel layer.

Materials other than the non-aqueous absorbent (B) may coexist in a gellayer in the present invention. Examples of the materials include aresin which absorbs the percutaneous absorption drug, an ingredienthaving warm-feeling, a representative of which is capsaicin derived fromCapsicum annuum L. for imparting warm-feeling effect and an analogthereof, an antiseptic, a fungicide, an antioxidant, a ultravioletabsorbing agent, a perfume and the like in addition to the (B), beingnot limiting. A method of allowing the aforementioned antiseptic,fungicide, antioxidant, ultraviolet absorbing agent, perfume and thelike to coexist is not particularly limited as long as percutaneousabsorption effect of the patch of the present invention and effects ofother coexisting materials are not prevented. For example, thesematerials may be mixed with a gel layer in advance, and coated on thesupport. Alternatively, these coexisting materials may be accommodatedin a layer different from a gel layer. In order to improve contactfeeling, the same polymer and thickener as those described for thealcohol-based bactericidal material may be added to the patch of thepresent invention.

Since the patch of the present invention contains the non-aqueousabsorbent (B) of the present invention, and can gelate a large amount ofpercutaneous absorption drug even at a small amount, it becomes possibleto retain a large amount of percutaneous absorption drug and, sinceanti-inflammatory effect lasts over a long time, the patch of thepresent invention can be suitably used as a patch.

[Insecticidal Compositions and Insecticides]

The insecticidal composition of the present invention comprises thenon-aqueous absorbent (B) of the present invention and a pyrethroidinsecticidal ingredient.

The pyrethroid insecticidal ingredient is not particularly limited aslong as it is liquid or solid. When the ingredient is liquid, it can beused as it is. When the ingredient is a liquid having a high viscosityand is hardly absorbable, or a solid, it may be dissolved in an alcoholsolvent (ethanol etc.), and absorbed in the non-aqueous absorbent (B).The concentration at dissolution may be adjusted depending on a usepurpose, being not particularly limited. When the pyrethroidinsecticidal ingredient is a solid having thermal meltability, it may beabsorbed in (B) after thermal melting.

In the present invention, specifically, examples of the pyrethroidinsecticidal ingredient include empenthrin, flamethrin, transfurthrin,teflamethrin, allethrin and prarethrin, and the ingredient may beappropriately selected depending on a utility and a purpose. Among them,preferable are empenthrin, flamethrin, transfurthrin and prarethrin, andmore preferable are empenthrin, transfurthrin and allethrin.

An amount of absorbing the pyrethroid insecticidal ingredient(hereinafter, insecticidal ingredient) of the insecticidal compositionof the present invention may be designed as in an amount of absorbing analcohol in the case of alcohol-based bactericidal material, being notproblematic.

When the insecticidal composition is shaped into a sheet, the sheet maybe as in the alcohol-based bactericidal material. In addition, athickness, a length and a width of a sheet; a substrate to be used, athickness of a substrate, a method of coating or impregnating asubstrate with the non-aqueous absorbent (B), and a basis weight may beas described above. Since the thus prepared insecticidal compositioncontains the sheet-like non-aqueous absorbent (B) of the presentinvention, and effectively absorbs the insecticidal ingredient, it isused as a sheet-type insecticide.

Another aspect is an integrated gelated-type insecticide comprising the(B) and an insecticidal ingredient. A ratio of the (B)/insecticidalingredient, a method of preparing the same in this integratedgelated-type insecticide may be as in the alcohol-based bactericidalmaterial.

A form of a gel comprising (B) and the insecticidal ingredient, and amethod of preparing the same may be as in the alcohol-based bactericidalmaterial.

In addition, in view of long term use, it is preferable to incorporate astabilizer into the insecticidal composition of the present invention.Further, if necessary, a volatilization adjusting agent, a solvent, aperfume, a pigment and the like may be appropriately added. As thestabilizer, stabilizers which are not substantially volatilized at aheating temperature of 50 to 200° C., such as dibutylhydroquinone,2,2′-methylenebis-(4-ethyl-6-t-butylphenol),4,4′-butylidenebis-(3-methyl-6-t-butylphenol),tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane,pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],stearyl-β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate,tris-(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate,4,4′-thiobis-(3-methyl-6-t-butylphenol), 2-mercaptobenzimidazole,trinonylphenyl phosphite and the like are preferable, and these may beused alone, or in combination of two or more.

The insecticide of the present invention is characterized in that theaforementioned insecticidal composition is accommodated in an externalmaterial, at least a part of which comprises a substrate through which asteam of an insecticidal ingredient can permeate (hereinafter, referredto as steam permeable substrate).

Herein, an insecticidal ingredient steam permeable substrate is asubstrate having an insecticidal ingredient steam permeability ofpreferably 0.1 g/m²·24 hr (50% RH/40° C.) or larger, more preferably 1g/m²·24 hr (50% RH/40° C.) or larger, further preferably 5 g/m²·24 hr(50% RH/40° C.) or larger. Herein, a steam permeability, definition, anda measuring method of the insecticidal ingredient, and a kind of amaterial may be the same as those of the aforementioned alcohol-basedbactericidal material.

In the aforementioned construction, a part of the substrate may beinsecticidal ingredient steam permeable. In this case, a substrate maybe such a sheet that contents are not leaked, and a material of thesubstrate is not particularly limited.

In the insecticide of the present invention, materials other than the(B) and the insecticidal ingredient may coexist in the externalmaterial. Examples of the materials include a resin which absorbs aninsecticidal ingredient, an insecticidal ingredient carrier such assilicon oxide, vermeculite and the like, an oxygen scavenger comprisingan iron powder and an oxidation promoter such as sodium chloride, analdehyde adsorbent such as polyallylamine and anionic exchange resin, anethylene absorbent, an ethylene generator, a perfume and the like, otherthan (B), being not limiting. A method of allowing the aforementionedoxygen scavenger, aldehyde adsorbent, ethylene adsorbent, ethylenegenerator, perfume and the like to coexist is not particularly limitedas long as the insecticidal effect of the insecticide of the presentinvention and effects of other coexisting materials are not prevented,and is as described for the alcohol-based bactericidal material.

A mode for carrying out the insecticidal composition and the insecticideof the present invention is not particularly limited, but theinsecticidal composition and/or the insecticide of the present inventionmay be used per se as a normal temperature volatilization type, or maybe formulated into a heating volatilization type and may be used byheating. A normal temperature volatilization insecticidal composition orinsecticide which can be used at a normal temperature may be filled, forexample, in a plastic container, and may be used by hanging in awardrobe, or a sheet-type insecticide may be wrapped with a Japanesepaper, and may be used by placing into a drawer.

In addition, when a heating volatilizing type is used by heating, forexample, this is filled into a plastic container, this is placed on aradiating plate which Ls heated at a temperature of 50 to 200° C., andis used by gradual volatilization of an insecticidal ingredient,thereby, insecticidal efficacy can be maintained for a long term. Atemperature of a radiating plate is preferably 50 to 200° C., morepreferably 60 to 190° C., further preferably 70 to 180° C. When thetemperature is 50° C. or higher, an insecticidal ingredient in a heatingvolatilization type is volatilized at a necessary amount. When thetemperature is 200° C. or lower, a gel is not deteriorated by heat.

Since the insecticidal composition of the present invention contains theaforementioned non-aqueous absorbent (B) as a constitutional component,and can gelate a large amount of insecticidal ingredient even at a smallamount, it becomes possible to retain a large amount of an insecticidalingredient and, since insecticidal effect lasts over a long term withoutfear of liquid leakage unlike the previous liquid insecticide, thecomposition can be suitably used as a normal temperature volatilizationtype or heating volatilization insecticidal composition.

In addition, since an insect-killing method of filling an insecticideobtained by accommodating the insecticidal composition of the presentinvention in an external material, at least a part of which comprises asubstrate through which a steam of an insecticidal ingredient canpermeate, into a plastic container, and hanging this in a wardrobe, andan insect-killing method of placing the container on a radiating platewhich is heated at a temperature of 50 to 200° C. have no fear ofpollution due to leakage of contents, and insecticidal effect lasts overa further long term by accommodating in an external material having aregulated steam permeation amount, those methods become an extremelyuseful heating volatilization insect-killing method.

[Fuel Stores for Fuel Batteries and Fuel Batteries]

The fuel store for fuel batteries (hereinafter, referred to as fuelstore) in the present invention comprises the non-aqueous absorbent (B)and a liquid fuel for fuel batteries, and the fuel battery uses thesame.

The liquid fuel for fuel batteries (hereinafter, referred to as liquidfuel) used in the present invention is not particularly limited as longas it is a fuel for fuel batteries which has previously been used.Preferably, the liquid fuel is a mixture of one or more selected fromthe group consisting of methanol, ethanol, hydrazine, formalin,liquified petroleum gas, naphtha, gasoline, kerosine, liquified naturalgas, and liquified dimethyl ether, or a mixture of this and water. Morepreferable are methanol, ethanol and a mixture of water and them.

An amount of absorbing a liquid fuel of the fuel store of the presentinvention may be designed as in an amount of absorbing an alcohol in thecase of the alcohol-based bactericidal material.

When the fuel store of the present invention is shaped into a sheet, thesheet may be as in the aforementioned sheet-like alcohol-basedbactericidal material. A thickness, a length and a width of a sheet; asubstrate to be used, a thickness of a substrate, a method of coating orimpregnating a substrate with the non-aqueous absorbent (B), and a basisweight may be as described above. Since the thus prepared liquid fuelstore for fuel batteries contains the sheet-like non-aqueous absorbent(B) of the present invention, and effectively absorbs the liquid fuelfor fuel batteries, this can be used as a sheet-like fuel store for fuelbatteries.

Another aspect is an integrated gelated-type fuel store comprising the(B) and a liquid fuel. A ratio of the (B)/liquid fuel, and a method ofpreparing the same in this integrated gelated-type fuel-stored may be asin the alcohol-based bactericidal material.

In addition, if necessary, one or more selected from the groupconsisting of other gelating agent (examples include the same gelatingagents as those described-above for the fuel composition for solidfuels), an adsorbent (dextrin, dextran, silica gel, silica, alumina,molecular sieve, kaolin, diatomaceous earth, carbon black, active carbonetc.), a thickener, a binder, and a material which chemical converts aliquid fuel into a non-flowing fuel may be incorporated in the fuelstore of the present invention. These are not particularly limited aslong as they exert their function, and may be solid or liquid. Inaddition, they may be incorporated at any stage of preparation of thefuel store.

In order to suppress volatilization of a fuel, another aspect is a fuelstore characterized in that the aforementioned fuel store isaccommodated in an external material comprising a substrate throughwhich a steam of a liquid fuel, preferably, a steam of methanol does notpermeate, and a fuel supply valve is attached to a part of thereof.

In the present invention, the aforementioned substrate through which asteam of a liquid fuel does not permeate is a substrate having a liquidfuel steam permeability, preferably, a methanol steam permeability ofpreferably 10 g/m²·24 hr (50% RH/40° C.) or smaller, more preferably 1g/m² 24 hr (50% RH 40° C.) or smaller, further preferably 0.1 g/m²·24 hr(50% RH; 40° C.). Definition and a measuring method of a liquid fuelsteam permeability are as in the case of the alcohol-based bactericidalmaterial.

Examples of the material used in the aforementioned substrate includematerials described for the cool insulating material, a metal can suchas an aluminum can and a laminate thereof, a laminate of theaforementioned plastic film, the aforementioned metal film and theaforementioned metal can, and a laminate of them and a paper, anon-woven fabric, a woven fabric or the like. Such the substrate is notparticularly limited as long as it is a substrate having liquid fuelsteam impermeability and no leakage of contents.

Alternatively, if necessary, a substrate may be subjected to waterresistance treatment, oil resistance treatment or printing.

In addition, when an external material is a monolayer, it is notparticularly limited as long as a liquid fuel steam permeability is inthe aforementioned range. In addition, even when an external material isa laminate, the number of layers is not particularly limited as long asa liquid fuel steam permeation is in the aforementioned rangePreferably, the number of layers is 2 to 5. More preferably, the numberof layers is 2 to 3. Alternatively, different kinds of materials may becombined.

Materials which are allowed to coexist in an external material for thefuel store, and the laminated sheet may be as in thealcohol-bactericidal material.

Examples of a method of releasing a liquid fuel from the fuel store ofthe present invention include the following methods (i) to (iv). As longas a necessary amount of a fuel is released at a necessary time, themethod is not limited to them. Alternatively, two or more of thesemethods may be combined.

(i) A method of heating a fuel tank to release a fuel from a fuel store,and supplying the fuel to a fuel electrode.

(ii) A method of compressing a fuel tank to release a fuel from a fuelstore, and supplying the fuel to a fuel electrode.

(iii) A method of heating a fuel store which is mounted in place of afuel tank, to release a fuel, and supplying the fuel to a fuelelectrode.

(iv) A method of compressing a fuel store which is mounted in place of afuel tank, to release a fuel store, and supplying a fuel to the fuelelectrode.

Another invention is a fuel battery comprising the non-aqueous absorbent(B) and a liquid fuel for fuel batteries. In particular, the fuelbattery of the present invention is suitable in a methanol-type fuelbattery.

Usually, a methanol-type fuel battery is composed of a fuel electrode,an air electrode, an electrolyte layer, a fuel tank, an air tank, a fuelsupplying port, an air supplying port, an outlet for discharging areaction product gas, an outlet for discharging a reaction productsubstance and the like. As a liquid fuel, an aqueous methanol solutionis mainly used, and a liquid fuel is sent from a fuel tank to a fuelelectrode. In the present invention, it is preferable that a fuelbattery is formed by the method of (v) or (vi).

(v) A method of using the non-aqueous absorbent (B) and/or a fuel storein a line from a fuel tank to a site contacting directly with a fuelelectrode and/or contacting indirectly with a fuel electrode via avolatilizing layer.

(vi) A method of using the non-aqueous absorbent (B) in an electrolytelayer.

In the case of (v), the non-aqueous absorbent (B) is present in a fuelsupplying line from a fuel tank to a fuel electrode, and an aqueousmethanol solution is filled therein. When the non-aqueous absorbent (B)is directly contacted with a fuel electrode, a fuel oozes out graduallyfrom a contact surface and is supplied to a fuel electrode, and is usedin a reaction. When the non-aqueous absorbent (B) is indirectlycontacted with a fuel electrode via a volatilizing layer, a liquid fuelis supplied from the non-aqueous absorbent (B) and/or a fuel store tothe volatilizing layer, volatilized in the volatilizing layer, and agaseous fuel is supplied to a fuel electrode and is used in a reaction.Since occurrence of bubbles during a long unused term or occurrence ofbubbles due to exothermic heat during battery working can be preventedby gelating a fuel in a fuel supplying line using the non-aqueousabsorbent (B), it becomes possible to retain an amount of supplying afuel to a fuel electrode constant. Thereupon, a shape of the non-aqueousabsorbent (B) is not particularly limited as long as a liquid fuel canbe absorbed and gelated, but preferably is particulate or sheet-like.

In the method of (vi), crossover of methanol which is one of mostimportant problems to a methanol battery can be prevented. That is,since a fuel which has became excessive at a fuel electrode is permeatedto an air electrode via an electrolyte layer, a fuel is directlyoxidized on an air electrode, and the deterioration of the performanceof an air electrode can be considerably suppressed. In this case, thenon-aqueous absorbent (B) may be located at any position of a fuelbattery as long as a fuel permeating through an electrolyte layer can beabsorbed, but preferably located between a fuel electrode and an airelectrode and/or at a contact surface between a fuel electrode and anelectrolyte layer. A shape of the non-aqueous absorbent (B) is notparticularly limited, but any shape may be used as long as a fuelpermeating through an electrolyte layer can be absorbed. Preferable issheet-like.

In the fuel battery of the present invention, other materials, forexample, a fuel permeating plate (carbon porous plate etc.) may coexistin order to permeate a fuel, or the previous ion exchange membrane(copolymer of tetrafluoroethylene and perfluorovinyl ether etc.) maycoexist in order to arrest crossover of a fuel. A method of allowingthose materials to coexist is arbitrary as long as their function is notprevented.

Since the sheet-type fuel store, the integrated gelated-type fuel store,and the fuel store obtained by accommodating in an external materialcomprising a substrate through which a steam of their liquid fuel doesnot permeate, of the present invention, contains the non-aqueousabsorbent (B) of the present invention, and can gelate a large amount ofliquid fuel for fuel batteries even at a small amount, it becomespossible to retain a large amount of a liquid fuel for fuel batteriesand, since a discharging time lasts for a long time, this can besuitably used as a fuel store.

In addition, since in the fuel battery provided with the non-aqueousabsorbent (B), when the non-aqueous absorbent (B) is used in a fuelsupplying line, a problem of unstabilization of a fuel supplying amountdue to occurrence of bubbles is solved and, when used in an electrolyte,crossover of a fuel does not occur, and reduction in properties of anair electrolyte can be suppressed, it becomes possible to make a fuelbattery which is stable over a long term and, thus, this is particularlysuitable in a methanol-type fuel battery.

The following Examples and Comparative Examples further illustrate thepresent invention, but the present invention is not limited by them.

Hereinafter, unless otherwise indicated, % indicates % by weight.

Example 1

360 Grams (5 mole) of acrylic acid, 1.08 g of pentaerythritol triallylether and 1140 g of water were placed into a 2 liter thermal insulatingpolymerization tank.

A temperature of a monomer solution was cooled to 0° C., nitrogen wasbubbled through the solution to reduce dissolved oxygen, and 0.36 g of2,2′-azobis(2-amidinopropane)hydrochloride, 3.1 g of a 35% aqueoushydrogen peroxide and 0.38 g of L-ascorbic acid as a polymerizationinitiator were added to initiate polymerization.

After polymerization, the produced hydrous gel was subdivided using ameat chopper and, thereafter, to this gel was added 1353 g (4 mole) of a60% methanol solution of methylcarbonate of1,2,3,4-trimethylimidazolinium cation (molecular weight: 203)(manufactured by Sanyo Chemical Industries, Ltd.), and occurrence ofdecarbonization and demethanolation was observed.

A hot air at 100° C. was permeated through the gel with imidazoliniumcation added thereto using a band-drier (permeating drier manufacturedby Inoue Kinzoku), water used as a solvent and methanol produced as aside produce were distilled off, followed by drying.

The dry material was ground using a cutter mill to obtain a particulatenon-aqueous absorbent (B1) comprising a crosslinked body (A1) in thepresent invention having an average particle diameter of 400 μm.

Example 2

According to the same manner as that of Example 1 except that 3307 g(4.5 mole) of a 20% aqueous solution of triethylammonium hydroxide(molecular weight: 147) (manufactured by Sanyo Chemical Industries,Ltd.) was added in place of methylcarbonate of1,2,3,4-trimethylimidazolinium cation used in Example 1, a non-aqueousabsorbent (B2) comprising a particulate crosslinked body (A2) of thepresent invention was obtained.

Example 3

184 Grams (1 mole) of p-styrenesulfonic acid, 104 g (1 mole) of styreneand 1.8 g of divinylbenzene were dissolved in 500 g of ethyl acetate.

To this monomer solution was added 332 g (0.8 mole) of a 45% ethanolsolution of monomethylcarbonate of 1-ethyl-3-methylimidazolium cation(molecular weight: 187) (manufactured by Sanyo Chemical Industries,Ltd.), to substitute a part of protons of sulfonic acid with imidazoliumcations.

Nitrogen was passed through this monomer solution to reduce dissolvedoxygen, the monomer solution was heated to 60° C. using a water bath,and a polymerization initiator solution in which 0.6 g ofazobis-2,4-dimethylvaleronitrile had been diluted with 12 g of ethanol,was added drop wise to perform polymerization. The resulting gelcontaining toluene was subdivided, and dried at 50° C. under reducedpressure of 100 hectopascal using a vacuum drier, to distill off thesolvent.

The dried material was ground using a cutter mill to obtain anon-aqueous absorbent (B3) comprising a particulate crosslinked body(A3) of the present invention having an average particle diameter of 400μm.

Comparative Example 1

According to the method described in Example 3 of JP-A No. 58-154709,100 g of a 80% aqueous solution of methacryloxyethyltrimethylammoniumchloride which is a monomer having a quaternary amino group, and 0.06 gof N, N-methylenbisacrylamide were mixed and, further, 0.8 g of2,2′-azobis(2-amidinopropane)hydrochloride as an initiator was added,followed by mixing.

This solution was placed into a box-type container heated by a constanttemperature water tank at 85° C., to perform polymerization. The polymerwas removed, and ground using a cutter mill to obtain a non-aqueousabsorbent (B′-1) comprising a comparative cationic crosslinked body(A′-1) having an average particle diameter of 400 μm.

Comparative Example 2

According to the method described in Example 1 of JP-A No. 60-179410gazette, 230 ml of cyclohexane and 1.0 g of ethylcellulose were placedinto a 500 ml round flask equipped with a stirrer, a condenser and anaddition funnel, and a temperature was risen to 75° C.

Separately, 12 g of acrylic acid, 26.2 g of dimethylaminoethylmethacrylate which is a tertially amino group-containing monomer, and 70g of distilled water were mixed in an Erlenmeyer flask and, further, 5 gof 35% hydrochloric acid and 0.5 g of N, N-methylenebisacrylamide wereadded to dissolve them uniformly.

To this monomer solution was added 0.02 g of ammonium persulfate as aninitiator, and this solution was added drop wise to the round flask over1.5 hours to perform polymerization.

After polymerization, cyclohexane was removed by decantation, and theresulting bead-like particles were dried at 90° C. using a vacuum drier,to obtain a non-aqueous absorbent (B′-2) comprising a comparativecrosslinked body (A′-2) having an average particle diameter of about 200micron.

Comparative Example 3

According to the method described in Example 1 of JP-A No. 3-221582gazette, 2 g of completely saponified POVAL, 0.8 g of partiallysaponified POVAL (saponification degree about 80%) and 300 g of waterwere placed into a 500 ml round flask equipped with a thermometer, a gasintroducing tube and a condenser, nitrogen was introduced therein tosubstitute dissolved oxygen, and the materials were heated to 40° C.

Thereafter, a solution containing 99.823 g of dodecyl acrylate which isa monomer, 0.177 g of ethylene glycol diacrylate which is a crosslinkingagent, and 0.5 g of azobis-2,4-dimethylvaleronitrile which is apolymerization initiator was added to the flask at once, followed byvigorously stirring at a stirring rate of 400 rpm. Then, a temperatureof an interior of the flask was risen to 70° C., polymerization wasperformed at that temperature for 2 hours and, thereafter, a temperaturein an interior of the flask was risen to 80° C., and the temperature wasmaintained for 2 hours to complete polymerization.

After polymerization, the bead-like crosslinked polymer was filtered,particles were washed with water, and dried to obtain a non-aqueousabsorbent (B′-3) comprising a particulate comparative crosslinked body(A′-3) having an average particle diameter of about 300 μm.

Comparative Example 4

According to the method described in Example 1 of JP-A No. 11-35632gazette, a mixed solution containing 99.827 g of methoxyethyl acrylate,0.173 g of hexanediol diacrylate which is a crosslinking agent, and 0.1g of azobis-2,4-dimethylvaleronitrile which is an initiator was pouredinto a glass cast polymerization container (thickness 1 cm) equippedwith a thermometer and a gas introducing tube, and the material washeated at 50° C. for 4 hours under a nitrogen stream, to performpolymerization. Thereafter, a temperature was risen to 80° C., and thistemperature was maintained for 2 hours to complete polymerization.

The polymer was cooled to 0° C., and ground with a cutter mill to obtaina non-aqueous absorbent (B′-4) comprising a comparative crosslinked body(A′-4) having an average particle diameter of about 500 μm.

Comparative Example 5

According to the method described in Example 8 of JP-A No. 4-230250, 40g of N-vinylacetamide and 2.0 mg of N, N′-1,4-butylenebisacetamide weredissolved in 150 g of water in a 200 ml three-neck separatable flaskequipped with a nitrogen introducing tube, a thermometer and an airdischarging port, in a bath maintained at 30° C., and nitrogen wasintroduced into the system at 1 liter/min to degas dissolved oxygen.Thereafter, 120 mg of 2,2′-azobis(2-amidinopropane)hydrochloridedissolved in 10 mg of degassed water was added, and allowed to stand for12 hours, to perform polymerization.

The resulting hydrous gel was cut with a mixer equipped with a cutter,washed with acetone, and vacuum-dried at 80° C. for 12 hours. Driedparticles were ground with a cutter mill to obtain a non-aqueousabsorbent (B′-5) comprising a comparative crosslinked body (A′-5) havingan average particle diameter of 400 μm.

Comparative Example 6

According to the same manner as that of Example 1 except that 226.7 g (4mole) of a 30% aqueous ammonia solution was used in the polymerized gelobtained in Example 1 in place of a 60% methanol solution ofmethylcarbonate of 1,2,3,4-trimethylimidazolinium cation (manufacturedby Sanyo Chemical Industries, Ltd.), a non-aqueous absorbent (B′-6)comprising a comparative crosslinked body (A′-6) having an averageparticle diameter of 400 μm was obtained.

An amount of absorbing and an amount of holding various organic solventsof the particulate non-aqueous absorbents (B1) to (B3) of the presentinvention and the non-aqueous absorbents (B′-1) to (B′-6) comprising thecomparative particulate crosslinked bodies were measured by thefollowing method. The results are shown in Table 1.

[Measurement of Liquid Absorbing Amount]

1.00 Gram of a particulate non-aqueous absorbent was added to a meshnylon bag (opening: 75 μm) having a width of 10 cm and a length of 20cm, the bag was immersed in propylene carbonate for 3 hours, andexcessive propylene carbonate was removed for 30 minutes. The sameprocedure was performed using an empty bag, and a liquid absorbingamount (g/g) was determined by the following equation.liquid absorbing amount (g/g)=weight of sample bag after swelling−weightof empty bag after immersion[Measurement of Liquid Holding Amount]

The mesh nylon bag after measurement of an absorbing amount was placedinto a centrifugation dehydrating apparatus (manufactured by Kokusan,centrifugation diameter 15 cm), and centrifugation-dehydrated at arotation rate of 1,500 rpm for 5 minutes. The same procedure was alsoperformed regarding an empty bag after immersion, and a liquid holdingamount was determined by the following equation.Liquid holding amount (g/g)=weight of sample bag afterdehydration−weight of empty bag after dehydration

Using γ-butyrolactone, methanol and toluene in place of propylenecarbonate, the same procedure was performed, and a liquid absorbingamount, and a liquid holding amount for each solvent was determined.TABLE 1 Propylene carbonate γ-butyrolactone Methanol Toluene LiquidLiquid Liquid Liquid absorb- Liquid absorb- Liquid absorb- Liquidabsorb- Liquid Non- ing holding ing holding ing holding ing holdingaqueous amount amount amount amount amount amount amount amountabsorbent (g) (g) (g) (g) (g) (g) (g) (g) Example 1 B1 300 260 160 188140 121 20 17 Example 2 B2 140 90 90 73 85 70 16 12 Example 3 B3 260 222190 162 110 83 65 50 Comparative B′-1 10 7 13 8 30 21 1 1 Example 1Comparative B′-2 12 8 10 7 49 29 2 1 Example 2 Comparative B′-3 5 3 12 813 8 17 14 Example 3 Comparative B′-4 12 9 13 8 14 10 1 1 Example 4Comparative B′-5 12 9 10 7 88 26 2 1 Example 5 Comparative B′-6 14 10 1511 27 20 1 1 Example 6

Example 4

72 Grams of acrylic acid, 28 g of monomethoxypolyethylene glycolacrylate (Blenmer AME-400, Nippon Oil & Fats Co., Ltd., number averagemolecular weight of PEG: about 400) and 100 g of methanol were placedinto a 1 liter round flask equipped with a stirrer, a nitrogenintroducing tube, a condenser, an addition funnel and a thermometer,nitrogen was passed through contents of the flask to substitutedissolved oxygen and, at the same time, a temperature of contents wasrisen to 50° C. using a water bath tank.

Separately, a solution obtained by dissolving 0.1 g ofazobis-2,4-dimethylvaleronitrile which is a polymerization initiator in9.9 g of methanol was added drop wise over about 2 hours using anaddition funnel while stirring under a nitrogen stream, to performpolymerization and, after completion of addition, polymerization wascontinued at 50° C. for 2 hours, and, thereafter, a temperature wasrisen to 70° C. to perform polymerization for 2 hours, andpolymerization was completed.

After a solution of the produced polymer was cooled to room temperature,322 g (corresponding to about 0.95 mole) of a 60% methanol solution ofmethyl carbonate of 1,2,3,4-trimethylimidazolinium cation (molecularweight 203) used in Example 1 was added drop wise to the polymersolution in the round flask using an addition funnel, and occurrence ofdecarbonization accompanied with addition was observed. After all amountof the imidazolinium cation solution was added drop wise, stirring wascontinued for about 2 hours to obtain a polymer solution (polymerconcentration: about 42%) substituted with imidazolinium cations.

To this polymer solution (100 g) was added 798 g of γ-butyrolactone, thematerial was heated to 60° C. under reduced pressure to distill offmethanol, and a γ-butyrolactone solution having the polymerconcentration of 5% was obtained.

To this γ-butyrolactone solution (100 g) was added 0.5 g of polyglycerolpolyglycidyl ether (Denacol 521, manufactured by Nagase Chemtex, numberof epoxy groups in molecule; 5) used in Example 4, this was placed intoa 100 ml sample bottle, the sample bottle was sealed, and the materialwas heated for 1 hour in a constant temperature tank at 70° C. toperform gelation, to obtain a non-aqueous gel (C1) comprising thenon-aqueous absorbent comprising a crosslinked body of the presentinvention and an organic solvent.

Comparative Example 7

In order to prepare a PEO (polyethylene oxide) system organicsolvent-containing gel, 3 g of polyethyleneglycol (molecular weight:400) monoacrylate and 2 g of polyethylene glycol diacrylate which arethe monomer and the crosslinking agent described in Example of JP-A No.6-68906 gazette, and 95 g of γ-butyrolactone as a solvent were mixed.

To this γ-butyrolactone solution having the monomer concentration of 5%was added 0.05 g of azobis(2,4-dimethylvaleronitrile) which is apolymerization initiator to dissolve them, and then, this was placedinto a 100 ml sample bottle, and polymerization was performed at 60° C.for 5 hours under a nitrogen stream, to obtain a comparative non-aqueousgel (C′-1) comprising a non-aqueous absorbent comprising a crosslinkedbody and an organic solvent.

Comparative Example 8

5 Grams of acryloyltrimethylammonium chloride and 0.1 g of N,N-methylenebisacrylamide as a crosslinking agent were dissolved in 95 gof γ-butyrolactone.

To this γ-butyrolactone solution having the monomer concentration of 5%was added 0.05 g of azobis-2,4-dimethylvaleronitrile which is apolymerization initiator to dissolve them, this was placed into a 100 mlsample bottle, and polymerization was performed at 60° C. for 5 hoursunder a nitrogen stream, to obtain a comparative non-aqueous gel (C′-2)comprising a non-aqueous absorbent comprising a crosslinked body and anorganic solvent.

Regarding the non-aqueous gel (C1) of the present invention prepared inExample 4, and comparative non-aqueous gels (C′-1) and (C′-2) preparedin Comparative Examples 7 and 8, the gelated states immediately afterpreparation and after with time were measured by the following method.The results are shown in Table 2.

[Method of Measuring Gelated States Immediately After Preparation andAfter with Time]

The prepared gels were observed, and assessed by the following criteriato obtain the gelated state immediately after preparation.

-   ⊚: Whole is completely gelated, and a gel strength is high.-   ◯: Whole is completely gelated, but a gel strength is low-   Δ: A gel is in semi-dissolved state and, when a sample bottle is    inverted, a gel flows.-   X: Whole is liquid, and is not gelated.

A sample bottle containing the prepared gel was completely sealed,heated for 30 days in a constant temperature tank at 80° C., and thestate of a gel after heating was adopted as gelated state after withtime.

Example 5

18.4 Grams (0.1 mole) of styrenesulfonic acid and 41.8 g (correspondingto 0.102 mole) of a 45% ethanol solution of monomethylcarbonate of1-ethyl-3-methylimidazolium cation used in Example 3 were added, tocompletely substitute protons of sulfonic acid with imidazolium cations,and thereafter the material was heated under reduced pressure using arotary evaporator, to distill off ethanol as a solvent, and methanolproduced as a side product.

10 Grams of styrenesulfonic acid monomer in which protons werecompletely substituted with imidazolium cations was dissolved in 90 g ofpropylene carbonate in which LiPF₆ had been dissolved to theconcentration of 1 mol/L (7.2 g/L) in a glove box under an argon gasstream, and 0.1 g of trimethylolpropanetriallyl ether which is acopolymerizing crosslinking agent and 0.1 g ofazobis-2,4-dimethylvaleronitrile which is a polymerization initiatorwere added to dissolve them.

This monomer solution (monomer concentration: 10%) was placed into a 100ml sample bottle, an argon gas was poured into the monomer solution tosubstitute dissolved oxygen, the sample bottle was completely sealed,and heated for 5 hours in a constant temperature tank at 60° C., toobtain a non-aqueous gel (C2) comprising a non-aqueous absorbentcomprising a crosslinked body of the present invention and an organicsolvent.

According to the same manner as that described above except that themonomer concentration was 5%, and propylene carbonate in which LiPF₆ hadbeen dissolved to the concentration of 1.5 mol/L (10.8 g/L) was used, anon-aqueous gel (C3) of the present invention comprising a non-aqueousabsorbent comprising a crosslinked body of the present invention and anorganic solvent was obtained.

Comparative Example 9

According to the same manner as that of Example 5 except thatpolyethylene glycol (molecular weight: 400) monoacrylate was used inplace of styrenesulfonic acid in which protons was substituted withimidazolium cations, a comparative crosslinked non-aqueous gel (C′-3)having the monomer concentration of 10% comprising a non-aqueousabsorbent comprising a comparative crosslinked body and an organicsolvent, and a crosslinked non-aqueous gel (C′-4) having the monomerconcentration of 5% were obtained.

Comparative Example 10

According to the same manner as that of Example 5 except thatacryronitrile was used in place of styrenesulfonic acid in which protonswere substituted with imidazolium cations, a comparative crosslinkednon-aqueous gel (C′-5) having the monomer concentration of 10%comprising a non-aqueous absorbent comprising a crosslinked body and anorganic solvent, and a crosslinked non-aqueous gel (C′-6) having themonomer concentration of 5% were obtained.

Comparative Example 11

According to the same manner as that of Example 5 except thatacryloyltrimethylammonium chloride was used in place of styrenesulfonicacid in which protons were substituted with imidazolium cations, anon-aqueous gel (C′-7) crosslinked at the monomer concentration of 10%and a non-aqueous gel (C′-8) crosslinked at the monomer concentration of5%, comprising a non-aqueous absorbent comprising a comparativecrosslinked body and an organic solvent were obtained.

Regarding the non-aqueous gels (C2) to (C3) comprising a non-aqueousabsorbent of the present invention and an organic solvent obtained bythe method of Example 5, and non-aqueous gels (C′-3) to (C′-8)comprising a comparative non-aqueous absorbent and an organic solventobtained in the methods of Comparative Examples 9 to 11, the gelatedstates immediately after preparation and after with time were measuredby the aforementioned method, and an ionic conductivity of a gel wasmeasured by the following method. The results are shown in Table 2.

[Measurement of Ionic Conductivity of Gel]

The prepared gel was excised into a cylinder having a diameter of 1 cm,this gel was held between platinum electrode discs having a diameter of1 cm, and an ionic conductivity at 25° C. was measured using animpedance analyzer under the conditions of an application voltage of 0.5mV and a sweeping frequency of 5 to 13 MHz. TABLE 2 Gelated state IonicNon- Polymer Immediately After conductivity aqueous concentra- afterwith of gel Example gel Organic solvent tion % preparation time (ms/cm)Example 4 C1 γ-butyrolactone 5 ⊚ ⊚ — Example 5 C2 Propylene carbonate 10⊚ ⊚ 4.2 C3 Propylene carbonate 5 ⊚ ⊚ 7.9 Comparative C′-1γ-butyrolactone 5 Δ X — Example 7 Comparative C′-2 γ-butyrolactone 5 ◯ X— Example 8 Comparative C′-3 Propylene carbonate 10 ◯ Δ 3.5 Example 9C′-4 Propylene carbonate 5 X X Not gelated Immeasurable Comparative C′-5Propylene carbonate 10 ◯ Δ 3.6 Example 10 C′-6 Propylene carbonate 5 X XNot gelated Immeasurable Comparative C′-7 Propylene carbonate 10 ◯ X 3.2Example 11 C′-8 Propylene carbonate 5 X X Not gelated Immeasurable

Example 6

72 Grams of acrylic acid, 28 g of monomethoxypolyethylene glycolacrylate (Blenmer AME-400, manufactured by Nippon Oil & Fats Co., Ltd.,number average molecular weight of PEG: about 400) and 100 g of methanolwere placed into a 1 liter round flask equipped with a stirrer, anitrogen introducing tube, a condenser, an addition funnel and athermometer, nitrogen was passed through contents (f the flask tosubstitute dissolved oxygen and, at the same time, a temperature ofcontents was risen to 50° C. using a water bath.

Separately, a solution in which 0.1 g of azobis-2,4-dimethylvaleronitrile as a polymerization initiator had beendissolved in 9.9 g of methanol was added drop wise over about 2 hoursusing an addition funnel while stirring under a nitrogen stream topolymerize, and after completion of addition, polymerization wascontinued at 50° C. for 2 hours and, thereafter, a temperature was risento 70° C. to perform polymerization for 2 hours, and polymerization wascompleted.

After a solution of the produced polymer was cooled to room temperature,271 g (corresponding to about 0.8 mole) of a 60% methanol solution ofmethylcarbonate of 1,2,3,4-trimethylimidazolinium cation (molecularweight 203) used in Example 1 was added drop wise to the polymersolution in a round flask using an addition funnel, and occurrence ofdecarbonization accompanied with addition was observed. After theaddition of all imidazolinium cation solution was completed, stirringwas continued for about 2 hours to obtain a polymer solution (polymerconcentration: about 47%) substituted with imidazolinium cations.

To 100 g of this polymer solution substituted with imidazolinium cationswas added 0.047 g of polyglycelol polyglycidyl ether (Denacol 521,manufactured by Nagase Chemkex, number of epoxies: about 5) as acrosslinking agent, and materials were mixed, and thereafter this wascoated on a releasing paper at a thickness of 200 μm using a knifecoater, and heated and dried for 10 minutes using a circulating airdrier at 100° C., to crosslink a polymer and distill off the usedmethanol.

After drying, the releasing paper was removed from the polymer to obtaina non-aqueous absorbent sheet (D1) comprising the crosslinked body ofthe present invention having a thickness of about 80 μm. A basis weightof this sheet was measured, and was found to be about 100 g/m².

Example 7

A polyester/polyethylene non-woven fabric (Alucima A0404WTO,manufactured by Unitika) having a thickness of 47 μm was immersed in amixed solution of the polymer solution of imidazolinium cation obtainedin Example 4 and polyglycerolpolyglycidyl ether, and then, the immersednon-woven fabric was squeezed using a mangle so as to give an immersionamount of the polymer solution of about 100 g/m² and, thereafter, thiswas heated and dried for 15 minutes in a circulating air drier at 90°C., to obtain the non-aqueous absorbent sheet (D2) of the presentinvention having a basis weight of the non-aqueous absorbent of about 47g/m². A thickness of this sheet was measured, and found to be about 65μm.

Example 8

Polyethylene was sandwich-laminated on one surface of the non-wovenfabric used in Example 7 so as to give a thickness of about 10 μm, toprepare a laminate sheet (total thickness: about 55 μm).

The mixed solution of the polymer solution of imidazolinium cation andpolyglycerolpolyglycidyl ether obtained in Example 6 was coated on anon-woven fabric surface on which polyethylene was not laminated at abasis amount of the mixed solution of about 100 g/m² using a knifecoater.

Thereafter, this was heated and dried for 15 minutes in a circulatingair drier at 90° C. to obtain a non-aqueous absorbent sheet (D3) havinga basis weight of a non-aqueous absorbent of about 47 g/m². A thicknessof this sheet was measured, and was found to be about 75 μm.

Example 9

332 Grams (corresponding to 0.8 mole) of the 45% ethanol solution ofmonomethylcarbonate of 1-ethyl-3-methylimidazolium cation using inExample 3 was added to 84 g (1 mole) of methacrylic acid, to substituteprotons of methacrylic acid with imidazolium cations (monomerconcentration: about 41%).

To this monomer solution were added 0.1 g of trimethylolpropanetriacrylate which is a copolymerizing crosslinking agent and 0.3 g oft-butylperoxy neodecanoate (PerbutylND, manufactured by Nippon Oil &Fats Co., Ltd., 10 hour half life temperature: 46.5° C.) which is apolymerization initiator.

A polyester non-woven fabric (Appeal AN060) having a thickness of about400 μm was immersed into this monomer solution, and the non-woven fabricwas squeezed using a mangle so as to give an immersion amount of themonomer solution of 500 g/m².

This non-woven fabric impregnated with the monomer solution was placedinto a forward wind drier in which blast heated at 80° C. was stopped,and polymerization was immediately initiated. Polymerization wasperformed at this temperature for 30 minutes, and thereafter, blastingwas initiated, followed by heating for another 1 hour to completepolymerization. At the same time, ethanol as a solvent was distilled offto obtain a non-aqueous absorbent sheet (D4) containing a non-aqueousabsorbent was obtained.

A thickness of this absorbent sheet and a basis weight of thenon-aqueous absorbent comprising a crosslinked body of the presentinvention were measured, and a thickness was found to be about 450μ, anda basis weight of the non-aqueous absorbent was about 200 g/m².

Comparative Example 12

The non-woven fabric (Alcima A0404WTO) used in Example 7 was adopted asit was as a comparative sheet (D′-1).

Comparative Example 13

The non-woven fabric (Apeel AN040) used in Example 9 was adopted as itwas as a comparative sheet (D′-2).

Regarding the absorbent sheets (D1) to (D4) of the present inventiondescribed in Examples 6 to 9 and comparative sheets (D∝-1) and (D′-2)described in Comparative Examples 12 to 13, a liquid absorbing amountand a liquid holding amount, a liquid absorbing rate, strike-throughproperty and a strike-through rate of the non-aqueous absorbent sheetfor an organic solvent were measured by the following method.

[Measurement of Liquid Absorbing Amount and Liquid Holding Amount ofNon-Aqueous Absorbent Sheet]

Measurement of a liquid absorbing amount; A sheet cut into 5×5 cm wasimmersed in propylene carbonate for 3 hours, and then, the sheet wasfixed with a clip, excessive propylene carbonate was extracted for 30minutes, and a liquid absorbing amount (g/cm²) was determined by thefollowing equation.Liquid absorbing amount (g/cm ²)=weight of sheet after swelling/25 (cm²)

Measurement of liquid holding amount: The sheet after measurement of aliquid absorbing amount was placed into a nylon mesh bag, the bag wasplaced into a centrifugation dehydrating apparatus (manufactured byKokusan, centrifugation diameter 15 cm), centrifugation-dehydrated for 5minutes at a rotation speed of 1,500 rpm, and a liquid holding amountwas determined by the following equation.Liquid holding amount (g/cm ²)=weight of sample bag after dehydration(g)−weight of empty bag (g)/25(cm ²)

The same procedure was performed using γ-butyrolactone in place ofpropylene carbonate, a liquid absorbing amount and a liquid holdingamount were determined for each solvent.

[Measurement of Liquid Absorbing Rate]

A sheet cut into 5×5 cm was placed on a glass plate, and an end of thesheet was fixed with a cellophane tape so that the sheet was adhered tothe glass plate.

1.0 Gram of propylene carbonate was added to a center part of the sheetusing a dropper, and a time until an all amount of added propylenecarbonate was absorbed in the sheet was adopted as a liquid absorbingrate.

[Measurement of Strike-Through Property and Strike-Through Rate]

Five filters having a diameter of 12.5 cm (manufactured by AdvanteckToyo, NO. 2) were stacked, a sheet cut into 5×5 cm was placed thereon,1.0 g of propylene carbonate colored with a dye was added to a centralpart of the sheet using a dropper, and strike-through property ofpropylene carbonate absorbed in a filter through the sheet, onto a backof the sheet was assessed using the following criteria:

-   ⊚: No strike-through-   ◯: Scarce strike-through-   Δ: Slight strike-through-   X: Much strike-through

In addition, by measuring a weight of the filter before and after atest, a strike-through rate was obtained by the following equation.Strike-through rate (%) {weight of filter after test (g)−weight offilter before test (g))}/weight of added propylene carbonate (g)×100TABLE 3 Propylene carbonate γ-butyrolactone Non- Liquid LiquidStrike-through test aqueous absorb- Liquid absorb- Liquid Liquid Strike-Strike- absorbent ing holding ing holding absorbing through throughExample sheet amount amount amount amount rate (sec) property rateExample 6 D1 30 26 16 14 360 ◯ 0.8 Example 7 D2 20 16 10 8 2 Δ 6.2Example 8 D3 18 15 10 8 2 ⊚ 0 Example 9 D4 62 53 40 26 1 ◯ - Δ 3.2Comparative D′-1 0.5 0.03 0.5 0.03 2 X 82.6 Example 12 Comparative D′-21.6 0.05 1.7 0.05 1 X 52.3 Example 13

From Table 1, the following is apparent.

(1) The non-aqueous absorbents (B1) to (B3) of the present inventionhave a remarkably high liquid absorbing amount and a remarkably highliquid holding amount for a polar solvent such as propylene carbonate,γ-butyrolactone, methanol and the like as compared with comparativenon-aqueous absorbents (B′-1) to (B′-6). In particular, a difference isremarkable regarding propylene carbonate and γ-butyrolactone which areused as a solvent of an electrolyte solution.

(2) By making a polymer structure approach a structure of a solvent tobe absorbed, it is also possible to absorb or hold an organic solventhaving relatively low polarity such as toluene.

From Table 2, the following is apparent.

(1) Non-aqueous gels (C1) to (C3) of the present invention can form afirm gel having a high gel strength which contains a solvent such asγ-butyrolactone and propylene carbonate, even at the low concentrationof the non-aqueous absorbent, as compared with comparative non-aqueousgels (C′-1) to (C′-8).

(2) (C1) to (C3) are remarkably excellent in gel stability with time ascompared with (C′-1) to (C′-8).

(3) (C2) and (C3) containing a Li ion etc. have a higher ionicconductivity as compared with (C′-3) to (C′-8). In particular, since(C3) can form a firm gel having a high gel strength even in the systemwhere the concentration of a crosslinked body is low and theconcentration of a lithium ion is high, it is possible to considerablyincrease an ionic conductivity of a gel.

From Table 3, the following is apparent.

(1) Non-aqueous absorbent sheets (D1) to (D4) of the present inventionhave remarkably high liquid absorbing amount and liquid holding amountfor propylene carbonate and γ-butyrolactone as compared with comparativesheets (D′-1) and (D′-2). In particular, a difference is especiallyremarkable regarding liquid holding amount.

(2) (D1) to (D4) have remarkably low strike-through property andstrike-through rate of a sheet as compared with (D′-1) and (D′-2). Inparticular, the absorbent sheet (D3) of the present invention using anon-woven fabric laminated with a polyethylene sheet as a substrate hasno strike-through.

(Alcohol-Based Bactericidal Material, Cold Insulating Material, FuelComposition and Solid Fuel Using the Same, Fuel Store)

Examples 10 to 12, Comparative Examples 14 to 19

Various alcohol solvents described in Table 4 were absorbed in thenon-aqueous absorbents (B1) to (B3) of Examples 1 to 3, and thenon-aqueous absorbents (BA′-1) to (BA′-6) of Comparative Examples 1 to6, to obtain (BA1) to (BA3) which are the alcohol-based bactericidalmaterial, the cool insulating material, the fuel composition and thefuel store of the present invention, and (BA-1) to (BA′-6) which arecomparative alcohol-based bactericidal material, cold insulatingmaterial, fuel composition and fuel store.

Comparative Example 20

207 Grams (1 mmole) of 2-acrylamido-2-methylpropanesulfonic acid, 72 g(1 mole) of acrylic acid and 1.8 g of divinylbenzene were dissolved in500 g of a mixed solution of water/isopropyl alcohol (IPA)=50/50.

Nitrogen was passed through this monomer solution to reduce dissolvedoxygen, and then, the monomer solution was heated to 60° C. using awater bath, and a polymerization initiator solution obtained by diluting0.6 g of azobis-2,4-dimethylvaleronitirile with 12 g of ethanol wasadded drop wise to perform polymerization. The resulting gel containingan IPA aqueous solution was subdivided, and 160 g (1.6 mole) of a 40%aqueous sodium hydroxite (guaranteed reagent) solution was added tosubstitute a part of protons of sulfonic acid with sodium.

The gel substituted with sodium was dried at 120° C. under reducedpressure at 100 hectopascal using a vacuum drier, to distill off thesolvent.

The dried material was ground using a cutter mill to prepared aparticulate non-aqueous absorbent having an average particle diameter of400 μm, and an alcohol solvent was absorbed therein to obtain (BA′-7)which is comparative alcohol-based bactericidal material, coolinsulating material, fuel composition or fuel store.

Regarding (BA1) to (BA3) which are the alcohol-based bactericidalmaterial, the cool insulating material, the fuel composition and thefuel store of the present invention of Examples 10 to 12, and (BA′-1) to(BA′-7) which are comparative alcohol-based bactericidal material, coolinsulating material, fuel composition and fuel store of ComparativeExamples 14 to 20, a liquid absorbing amount and a liquid holding amountfor various alcohol solvents described in Table 4 were measured by thefollowing method. The results are shown in Table 4.

[Measurement of Liquid Absorbing Amount and Liquid Holding Amount]

Using a mixed solvent of ethanol/water (mixing ratio=50/50, 75/25 and100/0), methanol and IPA in place of propylene carbonate in theaforementioned [Measurement of liquid absorbing amount] and [Measurementof liquid holding amount], these amounts were measured according to theaforementioned manner. TABLE 4 Mixture of ethanol/water 50/50 75/25100/0 Methanol Isopropanol Liquid Liquid Liquid Liquid Liquid Liquidholding Liquid holding Liquid holding Liquid holding Liquid holdingUtility absorbing amount absorbing amount absorbing amount absorbingamount absorbing amount Example material amount (g) (g) amount (g) (g)amount (g) (g) amount (g) (g) amount (g) (g) Example 10 BA1 300 280 200180 150 139 220 201 120 107 Example 11 BA2 320 300 200 184 170 153 225197 125 112 Example 12 BA3 280 250 170 152 140 127 203 170 110 98Comparative BA′-1 20 18 21 18 20 17 23 20 20 17 Example 14 ComparativeBA′-2 23 19 21 18 20 16 22 18 19 16 Example 15 Comparative BA′-3 22 1520 17 19 15 21 15 20 16 Example 16 Comparative BA′-4 24 14 19 17 16 1420 14 21 13 Example 17 Comparative BA′-5 28 18 21 15 18 12 22 15 20 14Example 18 Comparative BA′-6 5 2 2 1 2 1 2 1 1 1 Example 19 ComparativeBA′-7 115 100 89 80 78 69 142 125 65 59 Example 20

From Table 4, the following is apparent.

(1) Non-aqueous absorbents (B1) to (B3) of the present invention haveremarkably high liquid absorbing amount and liquid holding amount forwater-soluble alcohols such as methanol, ethanol, isopropyl alcohol andthe like as compared with comparative non-aqueous absorbents (B′-1) to(B′-7).

(2) The non-aqueous absorbents of the present invention have remarkablyhigh liquid absorbing amount and liquid holding amount for a mixedsolvent of ethanol and water which is usually used as a disinfectant oran insecticide.

Therefore, the non-aqueous absorbent of the present invention can besuitably used as a alcohol-based bactericidal material, a coolinsulating material, a fuel composition or a fuel store.

Example 13

According to the same manner as that of Example 4, a polymer solution(polymer concentration: about 42%) substituted with imidazoliniumcations was obtained. 950 Grams of a mixed solvent ofethanol/water=60/40 was added to 100 g of this polymer solution todissolve the polymer, to obtain a solution having the polymerconcentration of 5%.

According to the same manner as that of Example 4, 0.5 g of(aforementioned) polyglycerolpolyglycidyl ether was added to 100 g ofthis mixed solution to obtain an alcohol-based bactericidal material(BC1) comprising a non-aqueous absorbent and an alcohol solvent.

Separately, according to the same manner except that 950 g of a mixedsolvent of ethanol/water/sodium chloride=47.5/47.5/5 was used in placeof 950 g of a mixed solvent of ethanol/water=60/40, an integratedgelated-type cold insulating material (BC2) comprising a non-aqueousabsorbent and an alcohol solvent was obtained.

Separately, according to the same manner except that 950 g of a mixedfuel of ethanol/water=50/50 was used in place of 950 g of a mixedsolvent of ethanol/water=60/40, an integrated gelated-type fuelcomposition (BC3) was obtained.

Separately, according to the same manner except that 950 g of a mixedfuel of methanol/water=50/50 was used in place of 950 g of a mixedsolvent of ethanol/water=60/40, an integrated gelated-type fuel store(BC4) was obtained.

Comparative Example 21

In order to prepare a PEO (polyethylene oxide)-based alcoholsolvent-containing gel, 3 g of polyethylene glycol (molecular weight:400) monoacrylate and 2 g of polyethylene glycol diacrylate which arethe monomer and the crosslinking agent described in Example of JP-A No.6-68906 gazette, and 95 g of a mixed solvent of ethanol/water=60/40 as asolvent were mixed.

0.05 Gram of azobis-2,4-dimethylvaleronitrile which is a polymerizationinitiator was added to this solution having the monomer concentration of5% to dissolve the material, this was placed into a 100 ml samplebottle, and polymerization was performed at 60° C. for 5 hours under anitrogen stream to obtain a comparative integrated gelated-typealcohol-based bactericidal material (BC′-1) comprising a comparativenon-aqueous absorbent and an alcohol solvent.

Separately, according to the same manner as that of Example 13 exceptthat each mixed solvent was used, integrated gelated-type coolinsulating material (BC′-2), fuel composition (BC′-3) and fuel store(BC′-4) were obtained.

Comparative Example 22

5 Grams of N-vinylacetamide and 0.1 g of N,N-methylenebisacrylamide as acrosslinking agent were dissolved in 95 g of a mixed solvent containing5% of ethanol/water=60/40.

0.05 Gram of azobis(2,4-dimethylvaleronitrile) which is a polymerizationinitiator was added to this solution having the monomer concentration of5% to dissolve the material, this was placed into a 100 ml samplebottle, and polymerization was performed at 60° C. for 5 hours under anitrogen stream to obtain a comparative integrated gelated-typealcohol-based bactericidal material (BC′-5) comprising a comparativenon-aqueous absorbent and an alcohol solvent.

Separately, according to the same manner as that of Example 13 exceptthat each mixed solvent was used, integrated gelated-type coolinsulating material (BC′-6), fuel composition (BC′-7) and fuel store(BC′-8) were obtained.

Regarding (BC1) to (BC4) which are the integrated gelated-typealcohol-based bactericidal material, cool insulating material, fuelcomposition material and fuel store material of the present inventionprepared in Example 13, and (BC′-1) to (BC′-8) which are comparativeintegrated gelated-type alcohol-based bactericidal material, coolinsulting material fuel composition and fuel store prepared inComparative Examples 21 and 22, gelated states immediately afterpreparation and after with time were measured as described above. Theresults are shown in Table 5. TABLE 5 Gelated state Polymer ImmediatelyUtility concentration after After Example material Alcohol solvent (%)preparation with time Example 18 BC1 Ethanol/water = 60/40 5 ⊚ ⊚ BC2Ethanol/water/sodium 5 ⊚ ⊚ chloride = 47.5/47.5/5 BC3 Ethanol/water =50/50 5 ⊚ ⊚ BC4 Methanol/water = 60/40 5 ⊚ ⊚ Comparative BC′-1Ethanol/water = 60/40 5 Δ X Example 21 BC′-2 Ethanol/water/sodium 5 Δ Xchloride = 47.5/47.5/5 BC′-3 Ethanol/water = 50/50 5 Δ X BC′-4Methanol/water = 60/40 5 Δ X Comparative BC′-5 Ethanol/water = 60/40 5 ◯X Example 22 BC′-6 Ethanol/water/sodium 5 ◯ X chloride = 47.5/47.5/5BC′-7 Ethanol/water = 50/50 5 ◯ X BC′-8 Methanol/water = 60/40 5 ◯ X

From Table 5, the following is apparent.

(1) The integrated gelated-type alcohol-based bactericidal material,cool insulating material, fuel composition and fuel store of the presentinvention have a higher strength of a gel containing a solvent such asethanol alone and a mixed solvent of ethanol and water, and are firmeven at the low concentration of a crosslinked body (polymer) ascompared with comparative integrated gelated-type alcohol-basedbactericidal material, cool insulating material, fuel composition andfuel store.

(2) The integrated gelated-type alcohol-based bactericidal material,cool insulating material, fuel composition and fuel store of the presentinvention are remarkably excellent in stability after with time, ascompared with comparative integrated gelated-type alcohol-basedbactericidal material, cool insulating material, fuel composition andfuel store.

Example 14

According to the same manner as that of Example 6, a polymer solution(polymer concentration: about 47%) substituted with imidazoliniumcations was obtained. 0.047 Gram of the aforementionedpolyglycerolpolyglycidyl ether (Denacol 521, described above) which is areactive crosslinking agent was added to 100 g of this polymer solutionsubstituted with imidazolinium cations, to mix them, the mixture wascoated on a releasing paper at a thickness of 200 μm using a knifecoater, and heated and dried for 10 minutes using a circulating airdrier at 10° C. to perform crosslinking of the polymer and, at the sametime, distill off the used methanol. After drying, the releasing paperwas removed from the polymer to obtain (BD1) which is the sheet-typealcohol-based bactericidal material, cool insulating material, fuelcomposition or fuel store having a thickness of about 80 μm. A basisweight of this sheet (BD1) was about 100 g/m².

Example 15

The non-aqueous absorbent sheet (D2) obtained in Example 7 was adoptedas (BD2) which is a sheet-type alcohol-based bactericidal material, coolinsulating material, fuel composition or fuel store.

Example 16

The non-aqueous absorbent sheet (D4) obtained in Example 9 was adoptedas (BD3) which is a sheet-type alcohol-based bactericidal material, coolinsulating material, fuel composition or fuel store.

Comparative Example 23

The non-woven fabric (Alcima A0404WTO) used in Example 7 was adopted asit was as (BD′-1) which is a comparative sheet-type alcohol-basedbactericidal material, cool insulating material, fuel composition orfuel store.

Comparative Example 24

The non-woven fabric (Apeel AN040) used in Example 9 was adopted as itwas as (BD′-2) which is a comparative sheet-type alcohol-basedbactericidal material, cool insulating material, fuel composition orfuel store.

Comparative Example 25

80 Grams (0.8 mole) of a 40% aqueous sodium hydroxide (guaranteedreagent) solution was added to 184 g (1 mole) of p-styrenesulfonic acidto substitute a part of protons with sodium ions, and then, 104 g (1mole) of styrene, 1.8 g of divinylbenzene and 0.6 g ofazobis-2,4-dimethylvaleronitrile were added to dissolved them in 500 gof isopropyl alcohol.

To this monomer solution were added 0.1 g of trimethylolpropanetriacrylate which is a copolymerizing crosslinking agent and 0.3 g oft-butylperoxy neodecanoate (Perbutyl ND, manufactured by Nippon Oil &Fats Co., Ltd., 10 hour half life temperature: 46.5° C.) which is apolymerization initiator.

A polyester non-woven fabric (Posibul AK-65N) having a thickness ofabout 100 μm was impregnated with this monomer solution, and thenon-woven fabric was squeezed using a mangle so as to give animpregnation amount of the monomer solution of 300 g/m².

When this non-woven fabric impregnated with the monomer solution wasplaced into a forward air drier heated at 80° C. in which blasting wasstopped polymerization was immediately initiated. After polymerizationat this temperature for 30 minutes, blasting was initiated, and thematerial was further heated for 1 hour to complete polymerization and,at the same time, distill off ethyl acetate as a solvent, to obtain(BD′-3) which is a comparative sheet-type alcohol-based bactericidalmaterial, cool insulating material, fuel composition or fuel store.

A thickness of this sheet (BD′-3) was about 250 μm, and a basis weightwas about 100 g/m².

Regarding (BD1) to (BD3) which are the sheet-type alcohol-basedbactericidal material, cool insulating material, fuel composition andfuel store of the present invention described in Examples 14 to 16, and(BD′-1) to (BD′-3) which are comparative sheet-type alcohol-basedbactericidal material, cool insulating material, fuel composition andfuel store described in Comparative Examples 23 to 25, a liquidabsorbing amount and a liquid holding amount for various alcoholsolvents were measured by the following method. The results are shown inTable 6.

[Measurement of Liquid Absorbing Amount and Liquid Holding Amount ofAbsorbent Sheet]

According to the same manner except that a mixed solvent ofethanol/water (mixing ratio=50/50, 75/25 and 100/0), methanol or IPA wasused in place of propylene carbonate in the aforementioned [Measurementof liquid absorbing amount and liquid holding amount], a liquidabsorbing amount and a liquid holding amount for each solvent weremeasured. TABLE 6 Mixture of ethanol/water 50/50 75/25 100/0 MethanolIsopropanol Liquid Liquid Liquid Liquid Liquid Liquid holding Liquidholding Liquid holding Liquid holding Liquid holding Utility absorbingamount absorbing amount absorbing amount absorbing amount absorbingamount Example material amount (g) (g) amount (g) (g) amount (g) (g)amount (g) (g) amount (g) (g) Example 14 BD1 70 58 60 52 55 49 60 54 5548 Example 15 BD2 35 30 30 24 25 22 30 27 25 20 Example 16 BD3 120 100105 95 95 88 125 120 98 90 Comparative BD′-1 2 1 2 1 2 1 2 1 2 1 Example23 Comparative BD′-2 2 1 2 1 2 1 2 1 1 1 Example 24 Comparative BD′-3 1515 20 17 19 15 21 15 20 15 Example 25

From Table 6, the following is apparent.

(1) The sheet-type alcohol-based bactericidal material, cool insulatingmaterial, fuel composition and fuel store of the present invention havea remarkably higher liquid absorbing amount for ethanol alone or a mixedsolvent of ethanol and water, as compared with comparative sheet-typealcohol-based bactericidal material, cool insulating material, fuelcomposition and fuel store.

(2) The present invention has also remarkably high liquid absorbingamount and liquid holding amount for a mixed solvent of ethanol andwater which is usually used as a disinfectant, an insecticide or a coolinsulator.

(Alcohol-Based Bactericide)

Example 17

The non-aqueous absorbent (B1) obtained in Example 1 was uniformlyspread on a laminate film of rayon non-woven fabric (100g/m²)/polyethylene film (20 μm/) thin paper (16 g/m²) at a rate of 25g/m², an oil resistant paper (45 g/m²) was overlaid thereon, this wascut into 27 mm×27 mm square, heat-sealed, immersed in absolute ethanolfor 3 hours, and excessive absolute ethanol was extracted for 30 minutesto obtain an alcohol-based bactericide (E1).

Examples 18 to 19

According to the same manner as that of Example 17 except that theabsorbent sheet (D1) obtained in Example 6 or the integrated non-aqueousgel (C1) obtained in Example 4 was used in place of the non-aqueousabsorbent (B1) in Examples 17, an alcohol-based bactericide (E2) or (E3)was obtained.

Comparative Examples 26 to 28

According to the same manner as that of Example 17 except that thecomparative non-aqueous absorbent (B′-1) obtained in Comparative Example1, the comparative sheet (BD′-1) obtained in Comparative Example 23 orthe comparative sheet (BD′-2) obtained in Comparative Example 24 wasused in place of the non-aqueous absorbent (B1) in Example 17,comparative alcohol-based bactericides (E′-1), (E′-2) and (E′-3) wereobtained.

Comparative Example 29

A commercially available food freshness retaining agent Antimold 102(manufactured by Freund Corporation, bag size 45 mm×65 mm) containing0.6 g of ethanol was adopted as a comparative alcohol-based bactericide(E′-4).

Regarding the alcohol-based bactericides (E1) to (E3) of the presentinvention described in Examples 17 to 19, and comparative bactericides(E′-1) to (E′-4) shown in Comparative Examples 26 to 29, an ethanolreleasing test and a fungistatic effect test were performed by thefollowing method.

[Ethanol Releasing Test]

A moisture activity adjusting medium obtained by adding 100 g of waterto 3.9 g of potato dextrose and 75 g of sucrose and adjusting a pH withan aqueous NaOH solution was used. Moisture activity of this medium wasmeasured with a moisture activity measuring devise (manufactured byFreund Corporation; FWA-200), and was found to 0.90. Separately, abacterial solution was prepared by dissolving one platinum loop ofseparated Penicillum notatumu in 50 ml of a saline, and diluting 1 ml ofthis solution with 200 ml of a sterilized saline. Then, 1 ml of thebacterial solution was placed in a sterilized petri dish (diameter 95mm. depth 20 mm; manufactured by Aiken Kizai Co., Ltd.) and, then, about50 g of the aforementioned moisture activity adjusting medium was flowninto this petri dish. The bacterial solution and the medium were mixedin the petri dish, and the mixture was allowed to stand for 2 hours toobtain a bacterium seeding petri dish.

Two packing bags having an internal sizes of 155 mm×210 mm composed of afilm obtained by laminating a KOP film (polypropylene coated withpolyvinylidene chloride) and a LLDPE film (straight low densitypolyethylene) were prepared, any one of the above-obtained moldedproducts (E1) to (E3), and (E′-1) to (E′-4), and one bacterium seedingpetri dish were accommodated in each packing bag, and this washeat-sealed. The thus obtained three packing bags were allowed to standin a constant temperature bath at 25° C. and, 1, 5, 10, 15 and 20 daysafter allowing to stand, the concentration of an ethanol steam in thepacking bag was measured by the following method. The results are shownin Table 7.

Measurement of the concentration of an ethanol steam was performed usinggas chromatography. The measuring conditions were as follows:

-   Measuring apparatus; GC-14A (FID) (manufactured by Simadzu    Corporation)-   Filler; PEG-20M 10%-   Carrier; Chromosorb WAW DMCS-   Column; SUS 2 m×3 mm-   Carrier gas; N₂ 1.4 kg/cm²    -   H₂ 1.0 kg/cm²    -   Air 1.0 kg/cm²-   Temperature of sample injecting part and detecting part; 150° C.-   Column temperature, 80° C.

In Table 7, the concentration of an ethanol steam is expressed by %.TABLE 7 Alcohol-based Lapsed days (day) Example insecticide 1 5 10 15 20Example 17 E1 0.32 0.55 0.54 0.49 0.45 Example 18 E2 0.50 0.52 0.60 0.570.54 Example 19 E3 0.45 0.75 0.73 0.65 0.59 Comparative E′-1 0.10 0.050.03 0.02 0.01 Example 26 Comparative E′-2 0.15 0.11 0.08 0.05 0.03Example 27 Comparative E′-3 0.18 0.14 0.10 0.08 0.05 Example 28Comparative E′-4 0.40 0.45 0.44 0.38 0.32 Example 29[Assessment of Fungistatic Effect]

Growth state of fungus in a bacterium seeding petri dish was assessedbased on the following criteria, and fungistatic effect was assessed.The results are shown in Table 8. In addition, the result of the casewhere only a bacterium seeding petri dish was placed in the packing bagis adopted Comparative Example 30. TABLE 8 1 5 10 20 Alcohol- ColonyColony Colony Colony based Determi- diameter Determi- diameter Determi-diameter Determi- diameter Example bacteriocide nation (mm) nation (mm)nation (mm) nation (mm) Example 17 E1 — — — — Example 18 E2 — — — —Example 19 E3 — — — — Comparative E′-1 — + 3 ++ 7 +++ 14 Example 26Comparative E′-2 — + 4 ++ 8 +++ 12 Example 27 Comparative E′-3 — + 2 ++4 +++ 12 Example 28 Comparative E′-4 — — — — Example 29 Comparative — ++5 ++ 10 +++ 13 +++ 16 Example 30— Growth of fungus is not recognized at all.+ Slight growth of fungus is recognized.++ Growth of fungus has progressed.+++ Growth of fungus has considerably progressed.

From Table 7 and Table 8, the following is apparent.

(1) The alcohol-based bactericide of the present invention has a greaterethanol releasing rate as compared with the previous freshness retainingagent.

(2) Further, the alcohol-based bactericide of the present invention canexert performance equivalent to or superior over that of the prior agentalso regarding fungistatic effect.

(Cold Insulator)

Example 20

Using a polyethylene (50 μm)/polyester (12 μm)/aluminum foil (7μm)/polyethylene (12 μm) laminate (ethanol gas permeability 0.7 g/m²under RH 50%, 40° C. and 24 hours) as a steam impermeable substrate, abag for a cold insulator was made. A gel-like cold insulating materialcomprising the 1 g of non-aqueous absorbent (B1) obtained in Example 1,5 g of sodium chloride and 95 g of a 50% aqueous ethanol solution wasplaced in the bag, and an opening portion was heat-sealed to obtain acold insulator (F1) of the present invention.

Examples 21 and 22

According to the same manner as that of Example 20 except that thenon-aqueous absorbent sheet (D1) or the non-aqueous gel (C1) obtained inExample 6 or 4 was used in place of the non-aqueous absorbent (B1) inExample 20, the cold insulators (F2) and (F3) of the present inventionwere obtained.

Comparative Examples 31 to 33

According to the same manner as that of Example 20 except that thecomparative non-aqueous absorbent (B′-1), sheet (D′-1) or non-aqueousgel (C′-2) obtained in Comparative Example 1, 12 or 8 was used in placeof the non-aqueous absorbent (B1) in Example 20, comparative coldinsulators (F′-1), (F′-2) and (F′-3) were obtained.

Regarding the cold insulators of the present invention of Examples 20 to22 and the comparative cold insulators of Comparative Examples 31 to 33,an alcohol volatilization test and a durability test of a cold insulatorwere performed by the following methods.

[Alcohol Volatilization Test]

Each cold insulator was heated to 40° C., decrease in a weight of thecold insulator was measured, an alcohol volatilization amount wasobtained, and a remaining weight rate of an aqueous ethanol solution wasobtained by the following equation. The results are shown in Table 9.Remaining weight rate (%)=(weight of cold insulator beforeheating/weight of cold insulator after heating)×100[Durability Test of Cold Insulator]

Each cold insulator was allowed to stand at −30° C. for 16 hours and at25° C. for 8 hours, and this procedure was repeated 100 times, and then,circumstance of water separation, touch feeling and softness wereassessed by the following criteria. The results are also shown in Table9. TABLE 9 Remaining weight rate of prepared solution (%) ColdInitiation After 2 After 1 After 2 After 3 Water Touch Example insulatorday weeks month months months separation feeling Softness Example 20 F1100 99.99 99.99 99.99 99.99 ◯ ◯ ◯ Example 21 F2 100 99.98 99.98 99.9799.97 ◯ ◯ ◯ Example 22 F3 100 99.99 99.99 99.99 99.99 ◯ ◯ ◯ ComparativeF′-1 100 99.98 99.97 99.97 99.96 Δ Δ Δ Example 31 Comparative F′-2 10099.98 99.98 99.97 99.97 Δ Δ X Example 32 Comparative F′-3 100 99.9799.96 99.95 99.95 X X X Example 33Water separation◯ No water separation.Δ Slight water separation.X Much water separation.Touch feeling◯ Better touch feeling.Δ Slightly hard.X Hard.Softness◯ Bent well.Δ Difficult to bent.X Is not bend.

From Table 9, the following is apparent.

(1) The cool insulator of the present invention causes no decrease in aweight and is stable over a long term.

(2) The cool insulator of the present invention is excellent incapability of absorbing an ethanol/sodium chloride aqueous solutionhaving the high concentration, causes no water separation, and isexcellent in touch feeling and softness, as compared with previous coolinsulator.

(Solid Fuel)

Example 23

Using a cellophane (20 μm)/polypropylene (20 μm)/polyethylene (40 μm)laminate (ethanol gas permeability of 0.5 g/m² under RH50%, 40° C. and24 hours) as a steam impermeable substrate, a bag for a solid fuel wasmade. A gel-like fuel composition comprising 2 g of the non-aqueousabsorbent (B1) and 98 g of a 80% aqueous ethanol solution was placedinto this bag, and an opening portion was heat-sealed to obtain thesolid fuel (G1) of the present invention.

Example 24

According to the same manner as that of Example 23 except that the sheet(BD1) of Example 14 was used in place of the non-aqueous absorbent (B1),the solid fuel (G2) of the present invention was obtained.

Example 25

According to the same manner as that of Example 23 except that theintegrated gelated-type fuel composition (BC3) of Example 13 was used inplace of the non-aqueous absorbent (B1) and a 80% aqueous ethanolsolution, the solid fuel (G3) of the present invention was obtained.

Comparative Examples 34 to 35

According to the same manner as that of Example 23 except that thenon-aqueous absorbent (B′-1) of Comparative Example 1 or the sheet(BD′-1) of Comparative Example 23 was respectively used in place of thenon-aqueous absorbent (B1), comparative solid fuels (G′-1) and (G′-2)were obtained.

Comparative Example 36

According to the same manner as that of Example 23 except that the sheet(BD′-2) of Comparative Example 24 was used in place of the non-aqueousabsorbent (B1) and a 80% aqueous ethanol solution, the comparative solidfuel (G′-3) was obtained.

Comparative Example 37

100 Grams of a commercially available solid fuel in a tube, as it was,was used as a comparative solid fuel (G′-4).

Regarding the solid fuels (G1) to (G3) of the present invention and thecomparative solid fuels (G′-1) to (G′-4), an alcohol fuel evaporationtest and a combustion test were performed by the following methods. Theresults are shown in Table 10.

[Alcohol Fuel Evaporation Test]

Each solid fuel was heated to 40° C., decrease in a weight of a solidfuel was measured, an amount of an evaporated alcohol fuel was obtained,and a remaining weight rate of an alcohol fuel was obtained by thefollowing equation.Remaining weight rate (%)=(weight of solid fuel before heating/weight ofsolid fuel after heating)×100[Combustion Fuel]

Each solid fuel was placed into a container made of an aluminum foil,this was ignited, a combustion time was measured, and at the same time,the status at combustion was observed and assessed based on thefollowing criteria. TABLE 10 Remaining weight rate of alcohol fuel (%)Solid Initiation After 2 After 1 After 2 After 3 Combustion CombustionExample fuel date weeks month months months time (min) state Example 23G1 100 99.99 99.99 99.99 99.99 30 ⊚ Example 24 G2 100 99.98 99.98 99.9799.97 28 ⊚ Example 25 G3 100 99.99 99.99 99.99 99.99 31 ⊚ ComparativeG′-1 100 99.98 99.97 99.97 99.96 14 X Example 34 Comparative G′-2 10099.98 99.98 99.97 99.97 15 X Example 35 Comparative G′-3 100 99.97 99.9699.95 99.95 13 X Example 36 Comparative G′-4 100 0 0 0 0 13 ◯ Example 37⊚ Clearly burnt while retaining a shape to the last.◯ On the way, a fuel slightly oozes out.Δ A fuel oozes out, a shape is slightly disintegrated.X A fuel oozes out, a shape is not retained at all.

From Table 10, the following is apparent.

(1) The solid fuel accommodated in a steam impermeable substrate of thepresent invention does not cause change in a weight due to evaporationof an alcohol fuel, and becomes a solid fuel excellent in long termstorage stability.

(2) Since the solid fuel accommodated in a steam impermeable substrateof the present invention can retain a large amount of alcohol fuel ascompared with the comparative solid fuels (G′-1) to (G′-3) and theprevious solid fuel (G′-4), a fuel does not ooze out during combustion,and combustion over a long term becomes possible.

(Gel Sheet for Cooling)

Examples 26 to 28

Various alcohol solvents described in Table 11 were absorbed in thenon-aqueous absorbents (B1) to (B3) of Examples 1 to 3 to obtain gellayers (L1) to (L3) of a gel sheet for cooling.

Comparative Examples 38 to 44

Various alcohol solvents described in Table 11 were absorbed in acommercially available crosslinked polyvinylcarboxylic acid amide-basedliquid absorbing resin NA010 (manufactured by SHOWA DENKO K.K.), thenon-aqueous absorbent (B′-5) of Comparative Example 5, a commerciallyavailable crosslinked sodium polyacrylate-based water-absorbing resinSanfresh ST-500D (manufactured by Sanyo Chemical Industries, Co., Ltd.),a commercially available gelatin, the non-aqueous absorbent (B′-3) ofComparative Example 3, the non-aqueous absorbent (B′-6) of ComparativeExample 6, and (BA′-7) of Comparative Example 20 to obtain gel layers(L′-1) to (L′7) of comparative gel sheets for cooling.

Regarding the gel layers (L1) to (L3) of gel sheets for cooling in thepresent invention, and gel layers (L′-1) to (L′-7) of comparative gelsheets for cooling, a liquid absorbing amount and a liquid holdingamount for various alcohol solvents were measured as in measurement of aliquid absorbing amount and a liquid holding amount of ethanol/water.The results are shown in Table 11. TABLE 11 Mixture of ethanol/water50/50 75/25 100/0 Methanol Isopropanol Gel Liquid Liquid Liquid LiquidLiquid Liquid Liquid Liquid Liquid Liquid layer of absorbing holdingabsorbing holding absorbing holding absorbing holding absorbing holdinggel amount amount amount amount amount amount amount amount amountamount Example sheet (g) (g) (g) (g) (g) (g) (g) (g) (g) (g) Example 26L1 300 280 200 180 150 139 220 201 120 107 Example 27 L2 320 300 200 184170 153 225 197 125 112 Example 28 L3 280 250 170 152 140 127 203 170110 98 Comparative L′-1 20 18 21 18 20 17 23 20 20 17 Example 38Comparative L′-2 23 19 21 18 20 16 22 18 19 16 Example 39 ComparativeL′-3 22 15 20 17 19 15 21 15 20 16 Example 40 Comparative L′-4 24 14 1917 16 14 20 14 21 13 Example 41 Comparative L′-5 28 18 21 15 18 12 22 1520 14 Example 42 Comparative L′-6 5 2 2 1 2 1 2 1 1 1 Example 43Comparative L′-7 115 100 89 80 78 69 142 125 65 59 Example 44

Example 29

According to the same manner as that of Example 4, an integratedgelated-type gel layer (LC1) comprising a non-aqueous absorbent and analcohol solvent was obtained.

Comparative Example 45

According to the same manner as that of Comparative Example 7, anintegrated gelated-type gel layer (LC′-1) comprising a non-aqueousabsorbent and an alcohol solvent was obtained.

Comparative Example 46

According to the same manner as that of Comparative Example 22, anintegrated gelated-type gel layer (LC′-2) comprising a non-aqueousabsorbent and an alcohol solvent was obtained.

Regarding the aforementioned gel layer (LC1) of a sheet for cooling andthe gel layers (LC′-1) and (LC′-2) of the comparative sheets forcooling, gelated states immediately after preparation and after withtime were measured as described above. The results are shown in Table12. TABLE 12 Integrated Polymer Gelated state gelated-type concentrationImmediately After gel layer Alcohol solvent (%) after preparation withtime Example 29 LC1 Ethanol/water = 5 ⊚ ⊚ Comparative LC′-1 50/50 Δ XExample 45 Comparative LC′-2 ◯ X Example 46

Examples 30 to 32

According to the same manners as those of Examples 14, 7 and 9,sheet-type gel layers (LD1) to (LD3) were obtained.

Comparative Examples 47 to 49

According to the same manners as those of Comparative Examples 12, 13and 25, comparative sheet-type gel layers (LD′-1) to (LD′-3) wereobtained.

Regarding respective sheet-type gel layers of Examples 30 to 32, andComparative Examples 47 to 49, a liquid absorbing amount and a liquidholding amount for various alcohol solvents described in Table 13 weremeasured as described above. The results are shown in Table 13. TABLE 13Mixture of ethanol/water 50/50 75/25 100/0 Methanol Isopropanol LiquidLiquid Liquid Liquid Liquid Liquid Liquid Liquid Liquid Liquid Sheet-absorbing holding absorbing holding absorbing holding absorbing holdingabsorbing holding type gel amount amount amount amount amount amountamount amount amount amount Example layer (g) (g) (g) (g) (g) (g) (g)(g) (g) (g) Example 30 LD1 70 58 60 52 55 49 60 54 55 48 Examplc 31 LD235 30 30 24 25 22 30 27 25 20 Example 32 LD3 120 100 105 95 95 88 125120 98 90 Comparative LD′-1 2 1 2 1 2 1 2 1 2 1 Example 47 ComparativeLD′-2 2 1 2 1 2 1 2 1 2 1 Example 48 Comparative LD′-3 15 15 20 17 19 1521 15 20 15 Example 49

Example 33

The non-aqueous absorbent (B1) obtained in Example 1 was uniformlyspread on a rayon non-woven fabric (100 g/m²) at a ratio of 25 g/m², anoil resistant paper (45 g/m²) was overlaid thereon, this was cut into100 mm×100 mm square, heat-sealed, and 5.0 g of an aqueous ethanolsolution (ethanol/water=60:40) was absorbed therein to obtain the gelsheet for cooling (M1) of the present invention.

Example 34

5.0 Grams of an aqueous ethanol solution (ethanol/water=60/40) wasabsorbed in the sheet (BD1) obtained in Example 14, to obtain the gelsheet for cooling (M2) of the present invention.

Example 35

A rayon non-woven fabric was adhered on one surface of the non-aqueousabsorbent sheet (D4) of Example 9 with gum arabic, and 5.0 g of anaqueous ethanol solution (ethanol/water=60/40) was absorbed in thenon-aqueous absorbent sheet (D4), to obtain the gel sheet for cooling(M3) of the present invention.

Comparative Example 50

According to the same manner as that of Example 33 except that thegelated layer (L′-1) of the comparative gel sheet for cooling ofComparative Example 38 was used in place of the non-aqueous absorbent(B1), the comparative gel sheet for cooling (M′-1) was obtained.

Comparative Example 51

According to the same manner as that of Example 34 except that thesheet-type gel layer (LD′-3) of Comparative Example 49 was used in placeof the sheet, (BD1), the gel sheet for cooling (M′-2) was obtained.

Comparative Example 52

According to the same manner as that of Example 35 except that theintegrated gelated-type gel layer (LC′-1) of Comparative Example 45 wasused in place of the non-aqueous absorbent sheet (D4), the comparativegel sheet for cooling (M′-3) was obtained.

Regarding the gel sheets for cooling (M1) to (M3) of the presentinvention, and the comparative gel sheets for cooling (M′-1) to (M′-3),a cooling test and a freezing test were performed by the followingmethods. The results are shown in Table 14.

[Cooling Test]

Each gel sheet for cooling was allowed to stand for 1 hour in arefrigerator at 4° C. After taken out in a room, a temperature sensor(RTH-1010 manufactured by ESPEC Corporation) was mounted on a non-wovenfabric surface of the gel sheet, and a temperature of the surface wasmeasured with a thermorecorder (RS-11 manufactured by ESPEC Corporation)every hour until 6 hours passed.

[Freezing Test]

Each gel sheet for cooling was allowed to stand for 24 hours in arefrigerator at −18° C. After taken out in a room, the gel status wasjudged based on the following criteria. TABLE 14 Gel Temperature everyhour passage sheet for 0 Frozen cooling (hr) 1 2 3 4 5 6 status Example33 M1 4 7 10 14 18 22 25 ◯ Example 34 M2 4 6 9 12 15 20 24 ◯ Example 35M3 4 8 10 13 17 21 25 ◯ Comparative Example 50 M′-1 4 15 25 25 25 25 25Δ Comparative Example 51 M′-2 4 15 24 25 25 25 25 X Comparative Example52 M′-3 4 15 25 25 25 25 25 X◯ Not frozen.Δ Not frozen, but the sheet has no softness.X Frozen.

From Tables 11 to 14, the following is apparent.

(1) The gel sheet for cooling of the present invention has long lastingcooling capability.

(2) The gel sheet for cooling of the present invention is not frozeneven when stored in a refrigerator, and is excellent in softness.

(Fragrance Material and Fragrance)

Examples 36 to 38

Rosemary aromatic drugs described in Table 15 were absorbed in thenon-aqueous absorbents (B1) to (B3) of Examples 1 to 3, to obtainfragrance materials (N1) to (N3).

Comparative Examples 53 to 59

Rosemary aromatic drugs described in Table 15 were absorbed in acommercially available crosslinked polyvinylcarboxylic acid amide-basedliquid absorbing resin NA010 (SHOWA DENKO K.K.), the non-aqueousabsorbent (B′-5) of Comparative Example 5, a commercially availablecrosslinked sodium polyacrylate-based water-absorbing resin SanfreshST-500D (manufactured by Sanyo Chemical Industries Co., Ltd.),commercially available gelatin, the known-aqueous absorbent (B′-3) ofComparative Example 3, the non-aqueous absorbent (B′-6) of ComparativeExample 6, and (BA′-7) of Comparative Example 20, to obtain fragrancematerials (N′-1) to (N′-7).

Regarding a particulate non-aqueous absorbent in the fragrance materials(N1) to (N3) of the present invention of Examples 36 to 38, andfragrance materials (N′-1) to (N′-7) of Comparative Examples 53 to 59, aliquid absorbing amount and a liquid holding amount for various rosemaryaromatic drugs were measured as in the aforementioned measurement of aliquid absorbing amount and a liquid holding amount. The results areshown in Table 15. TABLE 15 Aromatic drug solution Mixture ofethanol/water/rosemary Methanol/rosemary IPA/rosemary 49/49/2 59/39/298/0/2 95/5 95/5 Liquid Liquid Liquid Liquid Liquid Liquid Liquid LiquidLiquid Liquid absorbing holding absorbing holding absorbing holdingabsorbing holding absorbing holding Fragrance amount amount amountamount amount amount amount amount amount amount material (g) (g) (g)(g) (g) (g) (g) (g) (g) (g) Example 36 N1 280 260 200 180 150 139 222201 120 107 Example 37 N2 270 240 200 184 170 153 225 197 125 112Example 38 N3 280 250 170 152 140 127 203 170 110 98 Comparative N′-1 2018 21 18 20 17 23 20 20 17 Example 53 Comparative N′-2 23 19 21 18 20 1622 18 19 16 Example 54 Comparative N′-3 22 15 20 17 19 15 21 15 20 16Example 55 Comparative N′-4 24 14 19 17 16 14 20 14 21 13 Example 56Comparative N′-5 28 18 21 15 18 12 22 15 20 14 Example 57 ComparativeN′-6 5 2 2 1 2 1 2 1 1 1 Example 58 Comparative N′-7 115 100 89 80 78 69142 125 65 59 Example 59

Example 39

740 Grams of a mixed solvent of ethanol/water/lemongrass oil=50/40/10was added to 100 g of a polymer solution (polymer concentration: about42%) substituted with imidazolinium cations obtained as in Example 4, todissolve the polymer, to obtain a solution having the polymerconcentration of 5%. 0.5 Gram of the aforementionedpolyglycerolpolyglycidyl ether used in Example 4 was added to 100 g ofthis mixed solution, this was placed into a 100 ml sample bottle, thesample bottle was sealed, heated for 1 hour in a constant temperaturebath at 70° C., to gelate the sample, to obtain the integratedgelated-type fragrance material (NC1) of the present invention with alemongrass oil aromatic drug absorbed therein.

Comparative Example 60

According to the same manner as that of Comparative Example 7 exceptthat a mixed solvent of ethanol/water/lemongrass oil=50/40/10 was usedin place of γ-butyrolactone as a solvent in Comparative Example 7, thecomparative integrated gelated-type fragrance material (NC′-1) wasobtained.

Comparative Example 61

According to the same manner as that of Comparative Example 22 exceptthat a mixed solvent of ethanol/water/lemongrass oil=50/40/10 was usedin place of a mixed solvent of ethanol/water=50/50 in ComparativeExample 22, the comparative integrated gelated-type fragrance (NC′-2)was obtained.

Regarding the aforementioned integrated gelated-type fragrance material(NC1) and the comparative integrated gelated-type fragrance materials(NC′-1) and (NC′-2), gelated states immediately after preparation andafter with time were measured as described above. The results are shownin Table 16. TABLE 16 Integrated Gelated status gelated-type PolymerImmediately fragrance Aromatic drug concentration after After materialsolution (%) preparation with time Example 39 NC1 Ethanol/water/ 5 ⊚ ⊚lemongrass oil = Comparative NC′-1 50/40/10 Δ X Example 60 ComparativeNC′-2 ◯ X Example 61

Examples 40 to 42

Cypress oil—based aromatic drugs described in Table 17 were absorbed inthe non-aqueous absorbent sheets (D1), (D2) and (D4) obtained inExamples 6, 7 and 9, to obtain the sheet-type fragrance materials (ND1)to (ND3) of the present invention.

Comparative Examples 62 to 64

Cypress oil—based aromatic drugs described in Table 17 were absorbed inthe sheets (D′-1) and (D′-2) used in Comparative Examples 12 and 13, andthe sheet (BD′-3) obtained in Comparative Example 25, the comparativesheet-type fragrance materials (ND′-1) to (ND′-3) were obtained.

Aromatic drugs described in Table 17 were absorbed in the sheet-typefragrance materials of Examples 40 to 42, and Comparative Examples 62 to64, and a liquid absorbing amount and a liquid holding amount weremeasured as described above. The results are shown in Table 17. TABLE 17Methanol/ Mixture of ethanol/water/cypress oil cypress oil IPA/cypressoil 49/49/2 74/24/2 98/0/2 95/5 95/5 Liquid Liquid Liquid Liquid LiquidLiquid Liquid Liquid Liquid Liquid Sheet- absorbing holding absorbingholding absorbing holding absorbing holding absorbing holding typeamount amount amount amount amount amount amount amount amount amountExample fragrance (g) (g) (g) (g) (g) (g) (g) (g) (g) (g) Example 40 ND170 58 60 52 55 49 60 54 55 48 Example 41 ND2 35 30 30 24 25 22 30 27 2520 Example 42 ND3 120 100 105 95 95 88 125 120 98 90 Comparative ND′-1 21 2 1 2 1 2 1 2 1 Example 62 Comparative ND′-2 2 1 2 1 2 1 2 1 1 1Example 63 Comparative ND′-3 15 15 20 17 19 15 21 15 20 15 Example 64

Example 43

The non-aqueous absorbent (B1) obtained in Example 1 was uniformlyspread on a rayon non-woven fabric (100 g/m²) at a ratio of 25 g/m², anoil resistant paper (45 g/m³) was overlaid thereon, this was cut into100 mm×100 mm square, heat-sealed and immersed in an aromatic drugsolution (ethanol/water/lemongrass oil=60/30/10) to obtain a fragrance(Q1).

Example 44

The non-aqueous absorbent sheet (BD1) obtained in Example 14 wasimmersed in an aromatic drug solution (ethanol/water/lemongrassoil=60/30/10) to obtain the fragrance (Q2) of the present invention.

Example 45

The integrated gelated-type fragrance material (NC1) of Example 39 wasadopted as a fragrance (Q3).

Comparative Example 65

According to the same manner as that of Example 43 except that thefragrance material (N′-1) of Comparative Example 53 was used in place ofthe non-aqueous absorbent (B1), the comparative fragrance (Q′-1) wasobtained.

Comparative Example 66

According to the same manner as that of Example 44 except that thesheet-type fragrance material (ND′-3) of Comparative Example 64 was usedin place of the non-aqueous absorbent sheet (BD1), the fragrance (Q′-2)was obtained.

Comparative Example 67

The integrated gelated-type fragrance material (NC′-1) of ComparativeExample 60 was adopted as a comparative fragrance (Q′-3).

Regarding the fragrances (Q1) to (Q3) of the present invention ofExamples 43 to 45, and the comparative fragrances (Q′-1) to (Q′-3) ofComparative Examples 65 to 67, a volatilization test was performed bythe following method.

[Volatilization Test]

The fragrances (Q1) to (Q3) and (Q′-1) to (Q′-3) were arranged on acenter of a bottom of a 50 liter plastic desiccator, and the desiccatorwas sealed. This was allowed to stand in a constant temperature constanthumidity bath regulated at a temperature of 28° C. and a relativehumidity of 60% RH. After 1, 2, 4, 8 and 12 weeks from the initiation ofthis allowing to stand, the desiccator was opened, a weight of afragrance every term was measured, and a volatilized amount (mg) wasdetermined. The results were shown in Table 18. TABLE 18 After 1 After 2After 4 After 8 After 12 Fragrance week weeks weeks weeks weeks Example43 Q1 20 mg 40 85 180 300 Example 44 Q2 18 37 75 150 240 Example 45 Q315 32 65 130 200 Comparative Q′-1 15 32 10 5 5 Example 65 ComparativeQ′-2 10 5 5 3 2 Example 66 Comparative Q′-3 7 4 4 2 1 Example 67

Example 46

According to the same manner as that of Example 43 except that thesheet-type fragrance material (ND1) of Example 40 was used in place ofthe non-aqueous absorbent (B1), the fragrance (Q4) of the presentinvention was obtained.

Example 47

According to the same manner as that of Example 43 except that theintegrated gelated-type fragrance material (NC1) of Example 39 was usedin place of the non-aqueous absorbent (B1), the fragrance (Q5) of thepresent invention was obtained.

Comparative Example 68

According to the same manner as that of Example 43 except that thesheet-type fragrance material (ND′-3) of Comparative Example 64 was usedin place of the non-aqueous absorbent (B1), the fragrance (Q′-4) wasobtained.

Comparative Example 69

According to the same manner as that of Example 43 except that theintegrated gelated-type fragrance material (NC′-1) of ComparativeExample 60 was used in place of the non-aqueous absorbent (B1), thecomparative fragrance (Q′-5) was obtained.

Regarding the fragrances (Q4) and (Q5) of the present invention ofExamples 46 to 47, and the comparative fragrances (Q′-4) to (Q′-5) ofComparative Examples 68 to 69, a volatilization test was performed as inthe aforementioned volatilization test. The results are shown in Table19. TABLE 19 After 1 After 2 After 4 After 8 After 12 After 24 Fragranceweek weeks weeks weeks weeks weeks Example 46 Q-4 15 mg 30 62 135 200420 Example 47 Q-5 12 25 52 100 150 320 Comparative Q′-4 14 13 12 8 5 3Example 68 Comparative Q′-5 6 4 4 2 1 1 Example 69

From Tables 15 to 19, the following is apparent.

Since the fragrance of the present invention has a large amount ofholding an aromatic drug, aroma releasing ability lasts over a longterm. Further, when used by accommodating in an external materialcomprising a steam permeable substrate, since a steam permeating amountcan be regulated, a fragrance which can maintain aroma effect for afurther long term can be provided.

(Patch Materials and Patches)

Examples 48 to 50

Percutaneous absorption drugs described in Table 20 were absorbed in thenon-aqueous absorbents (B1) to (B3) of Examples 1 to 3, to obtain patchmaterials (R1) to (R3).

Comparative Examples 70 to 76

Percutaneous absorption drugs described in Table 20 were absorbed in acommercially available crosslinked polyvinylcarboxylic acid amide-basedliquid absorbing resin NA010 (SHOWA DENKO K.K.), the non-aqueousabsorbent (B′-5) of Comparative Example 5, a commercially availablecrosslinked sodium polyacrylate-based water-soluble resin SunfrashST-500 D (manufactured by Sanyo Chemical Industries Co., Ltd.),commercially available gelatin, the non-aqueous absorbent (B′-3) ofComparative Example 3, the non-aqueous absorbent (B′-6) of ComparativeExample 6, and (BA′-7) of Comparative Example 20, to obtain patchmaterials (R′-1) to (R-7).

Regarding patch materials (R1) to (R3) of the present invention ofExamples 48 to 50, and the comparative patch materials (R′-1) to (R′-7)of Comparative Examples 70 to 76, a liquid absorbing amount and a liquidholding amount for mixed solvents described in Table 20 were measured asin the aforementioned liquid absorbing amount and liquid holding amount.The results are shown in Table 20. TABLE 20 Methanol/ Mixture ofethanol/indometacin indometacin Isopropanol/ 50/50 75/25 25/75 95/5indometacin Liquid Liquid Liquid Liquid Liquid Liquid Liquid Liquid 95/5absorbing holding absorbing holding absorbing holding absorbing holdingLiquid Liquid Patch amount amount amount amount amount amount amountamount absorbing holding Example material (g) (g) (g) (g) (g) (g) (g)(g) amount (g) amount (g) Example 48 R1 150 140 180 160 120 109 200 181100 87 Example 49 R2 160 100 180 164 100 83 202 181 94 14 Example 50 R3140 125 170 152 90 77 203 189 88 64 Comparative R′-1 20 18 21 18 20 1723 20 10 6 Example 70 Comparative R′-2 23 19 21 18 20 16 22 18 11 5Example 71 Comparative R′-3 22 15 20 17 19 15 21 15 10 4 Example 72Comparative R′-4 24 14 19 17 16 14 20 14 12 4 Example 73 ComparativeR′-5 10 4 15 7 8 3 11 5 10 5 Example 74 Comparative R′-6 5 2 2 1 2 1 2 11 1 Example 75 Comparative R′-7 15 7 20 11 12 4 18 9 12 7 Example 76

Example 51

740 Grams of a mixed solvent of ethanol/water/methyl salicylate=60/30/10was added to 100 g of a polymer solution (polymer concentration: about42%) substituted with imidazolinium cations obtained as in Example 4, todissolve the polymer, to obtain a solution having the polymerconcentration of 5%. To 100 g of this mixed solution was added 0.5 g ofthe aforementioned polyglycerolpolyglycidyl ether (described-above) usedin Example 4, this was placed into a 100 ml sample bottle, the samplebottle was sealed, the bottle was heated for 1 hour in a constanttemperature bath at 70° C. to gelate the material, to obtain theintegrated gelated-type patch material (RC1) of the present inventionwith methyl salicylate-based percutaneous absorption drug absorbedtherein.

Comparative Example 77

According to the same manner as that of Comparative Example 7 exceptthat a mixed solvent of ethanol/water/methyl salicylate=60/30/10 wasused in place of γ-butyrolactone as a solvent, the comparativeintegrated gelated-type patch material (RC′-1) was obtained.

Comparative Example 78

According to the same manner as that of Comparative Example 22 exceptthat a mixed solvent of ethanol/water/methyl salicylate=60/30/10 wasused in place of ethanol/water=60/40, the comparative integratedgelated-type patch material (RC′-2) was obtained.

Regarding the integrated gelated-type patch material (RC1) of Example 51and the comparative integrated gelated-type patch materials (RC′-1) and(RC′-2) of Comparative Examples 77 and 78, gelated states immediatelyafter preparation and after with time were measured as described above.The results are shown in Table 21. TABLE 21 Integrated Gelated statusgelated-type Polymer Immediately patch Percutaneous concentration afterAfter material absorption drug (%) preparation with time Example 51 RC1Ethanol/water/ 5 ⊚ ⊚ Comparative RC′-1 methyl Δ X Example 77 salicylate= Comparative RC′-2 60/30/10 ◯ X Example 78

Examples 52 to 54

Methyl salicylate-based percutaneous absorption drugs described in Table22 were absorbed in the non-aqueous absorbent sheets (D1), (D2) and (D4)obtained in Examples 6, 7 and 9, to obtain the sheet-type patchmaterials (RD1) to (RD3) of the present invention.

Comparative Examples 79 to 81

Methyl salicylate-based percutanesou absorption drugs described in Table22 were absorbed in the sheets used in Comparative Examples 12 and 13and the sheet-type gel layer (LD′-3) obtained in Comparative Example 49,to obtain the comparative sheet-type patch materials (RD′-1) to (RD′-3).

Regarding the sheet-type patch materials (RD1) to (RD3) of the presentinvention of Examples 52 to 54, and the comparative sheet-type patchmaterials (RD′-1) to (RD′-3) of Comparative Examples 79 to 81, a liquidabsorbing amount and a liquid holding amount were measured as in theaforementioned liquid absorbing amount and liquid holding amount. Theresults are shown in Table 22. TABLE 22 Mixture of ethanol/ Mixture ofMixture of ethanol/methyl salicylate methyl salicylate IPA/methylsalicylate 50/50 75/25 25/75 95/5 95/5 Liquid Liquid Liquid LiquidLiquid Liquid Liquid Liquid Liquid Liquid Sheet-type absorbing holdingabsorbing holding absorbing holding absorbing holding absorbing holdingpatch amount amount amount amount amount amount amount amount amountamount Example material (g) (g) (g) (g) (g) (g) (g) (g) (g) (g) Example52 RD1 70 58 60 52 55 49 60 54 50 41 Example 53 RD2 35 30 30 24 25 22 3027 25 20 Example 54 RD3 60 50 54 35 45 32 125 120 53 39 ComparativeRD′-1 2 1 2 1 2 1 2 1 2 1 Example 79 Comparative RD′-2 2 1 2 1 2 1 2 1 11 Example 80 Comparative RD′-3 12 8 11 7 10 5 15 10 10 4 Example 81

Example 55

The non-aqueous absorbent (B1) obtained in Example 1 was uniformlyspread on a rayon non-woven fabric (100 g/m²) at a ratio of 25 g/m², anoil resistant paper (45 g/m²) was overlaid thereon, cut into 100 mm×100mm square, heat-sealed, and immersed into a percutaneous absorption drug(ethanol/indometacin=50/50) to obtain a patch (S1).

Example 56

The non-aqueous absorbent sheet (BD1) obtained in Example 14 wasimmersed into a percutaneous absorption drug (ethanol/indometacin=50/50)to obtain a patch (S2).

Example 57

The integrated gelated-type patch material (RC1) of Example 51 wasadopted as an integrated gelated-type patch (S3).

Comparative Example 82

According to the same manner as that of Example 55 except that the patchmaterial (R′-1) of Comparative Example 70 was used in place of thenon-aqueous absorbent (B1), the comparative patch (S′-1) was obtained.

Comparative Example 83

According to the same manner as that of Example 55 except that asheet-type gel layer (LD′-3) of Comparative Example 49 was used in placeof the non-aqueous absorbent (B1), the patch (S′-2) was obtained.

Comparative Example 84

The integrated gelated-type patch material (RC′-1) of ComparativeExample 77 was adopted as a comparative patch (S′-3).

An amount of holding a percutaneous absorption drug for the patches (S1)to (S3) of the present invention of Examples 55 to 57, and thecomparative patches (S′-1) to (S′-3) of Comparative Examples 82 to 84was measured by the following method.

[Method of Measuring Amount of Holding Percutaneous Absorption Drug]

Each patch was sealed in an aluminum bag, stored under the condition of50° C., and a content of indometacin in each patch was measured by highspeed liquid chromatography initially, and 5 days, 10 days, 20 days and30 days after. Letting an initial content to be 1.00, a relative ratiois shown in Table 23. TABLE 23 Lapsed days Patch Initial 5 days 10 days20 days 30 days Example 55 S1 1.00 1.00 1.00 1.00 0.99 Example 56 S21.00 1.00 1.00 1.00 0.98 Example 57 S3 1.00 1.00 1.00 1.00 1.00Comparative S′-1 1.00 0.58 0.32 0.10 0.01 Example 82 Comparative S′-21.00 0.11 0.08 0.02 0.01 Example 83 Comparative S′-3 1.00 0.70 0.04 0.210.10 Example 84

Example 58

5.0 Grams of the non-aqueous absorbent (B1) obtained in Example 1, 2.25g of polyvinyl alcohol, 1.2 g of tartaric acid, 20 g of concentratedglycerin, 20 g of a 70% D-sorbitol solution, 3.0 g of kaolin, 0.1 g ofsodium edetate, 1.5 g of methyl salicylate and an appropriate amount ofa 60% aqueous ethanol solution were uniformly mixed to obtain anointment for patch. This ointment was spread on a non-woven fabric toobtain a patch (S4) according to the conventional method.

Example 59

According to the same manner as that of Example 58 except that thenon-aqueous absorbent (B2) of Example 2 was used in place of thenon-aqueous absorbent (B1), a patch (S5) was obtained.

Comparative Example 85

2.25 Grams of polyvinyl alcohol, 1.2 g of tartaric acid, 20 g ofconcentrated glycerin, 3.0 g of CMC, 5.0 g of partially neutralizedpolyacrylic acid, 20 g of a 70% D-sorbitol solution, 3.0 g of kaolin,0.1 g of sodium edetate, 0.08 g of methasilicate aluminate metal salt,1.5 g of methyl salicylate, and an appropriate amount of purified waterwere uniformly mixed to obtain an ointment for a patch. This ointmentwas spread on a non-woven fabric, to obtain the comparative patch (S′-4)by the conventional method.

Comparative Example 86

According to the same manner as that of Comparative Example 85 exceptthat a 60% aqueous ethanol solution was used in place of purified water,the comparative patch (S′-5) was obtained.

Comparative Example 87

According to the same manner as that of Comparative Example 85 exceptthat thermally crosslinked CMC used in Example 1 of JP-A No. 2000-95678gazette was used in place of CMC, and a 60% aqueous ethanol solution wasused in place of purified water, the comparative patch (S′-6) wasobtained.

Each of patches of Examples 58 to 69, and Comparative Examples 85 to 87was applied to panelers (male 5, female 5) appealing inferior limb pain,to attach one patch to an inferior limb pain place. Upon application for12 hours, comfortableness, effectiveness feeling, skin adherability, anda pain at peeling of a patch regarding each patch were assessed by thefollowing assessing methods. The results are shown in Table 24. TABLE 24Comfort- Effective- able- ness Skin Pain when Patch ness feelingadherability peeled Example 58 S4 ◯ ◯ ◯ ◯ Example 59 S5 ◯ ◯ ◯ ◯Comparative S′-4 Δ X ◯ Δ Example 85 Comparative S′-5 Δ X Δ DeterioratedExample 86 adherability Not assessed Comparative S′-6 Δ X ◯ Δ Example 87ComfortablenessAfter attachment of a patch, comfortableness one our later was assessedby the following 3 grades.◯ RefreshnessΔ Slight refreshnessX No refreshnessEffectiveness feelingAfter attachment of a patch, whether there remains effectiveness feeling12 hours later was assessed by the following 3 grades.◯ Effectiveness feelingΔ Slight effectiveness feelingX No effectiveness feelingSkin adherabilityUpon attachment of a patch, adherability to a skin was assessed by thefollowing 3 grades.◯Better adherabilityΔ Slightly peeled stateX No adherability, peeled statePain upon peelingA pain when a patch was peeled was assessed by the following 3 grades.◯ No pain is felt.Δ Slight pain is felt, but satisfactory level.X A half of peelers feel a pain.

From Table 20 to Table 24, the following is apparent.

(1) Whether the sheet-type or the integrated gelated-type, the patchmaterial of the present invention has a remarkably higher liquidabsorbing amount and liquid holding amount for a percutaneous absorptiondrug as compared with the comparative patch material.

(2) Since the integrated gelated-type patch material of the presentinvention is a firm gel having a higher gel strength which contains apercutaneous absorption drug, even at the lower concentration of anon-aqueous absorbent, as compared with the comparative integratedgelated-type patch material, stability of a gel with time is remarkablyexcellent.

(3) In the patch of the present invention, reduction in a content of acontained percutaneous absorption drug with time is suppressed, and alarge amount of a perucutaneous absorption drug can be stably retained.

(4) Since the patch of the present invention can contain a large amountof a percutaneous absorption drug, it is possible to have long lastingdrug efficacy such as inflammatory effect, analgesic effect and thelike.

(Insecticidal Compositions and Insecticides)

Examples 60 to 62

Pyrethroid insecticidal ingredients described in Table 25 were absorbedin the non-aqueous absorbents (B1) to (B3) of Examples 1 to 3, to obtaininsecticidal compositions (T1) to (T3).

Comparative Examples 88 to 94

Pyrethroid insecticidal ingredients described in Table 25 were absorbedin the non-aqueous absorbents (B′-1) to (B′-4) of Comparative Examples 1to 4, “Oleosoap PW-190” (acrylic polymer-based crosslinked polymer;manufactured by Nippon Shokubai Co., Ltd.), the non-aqueous absorbent(B′-6) of Comparative Example 6, and (BA′-7) of Comparative Example 20,to obtain comparative insecticidal compositions (T′-1) to (T′-7).

Regarding the non-aqueous absorbents of Examples 60 to 62, andComparative Examples 88 to 94, a liquid absorbing amount and a liquidholding amount were measured as in the aforementioned liquid absorbingamount and liquid holding amount. The results are shown in Table 25.TABLE 25 Methanol/allethrin Isopropanol/allethrin Mixture ofethanol/allethrin (or empenthrin) (or empenthrin) (or empenthrin) 50/5075/25 25/75 50/50 50/50 Liquid Liquid Liquid Liquid Liquid Liquid LiquidLiquid Liquid Liquid absorbing holding absorbing holding absorbingholding absorbing holding absorbing holding Insecticidal amount amountamount amount amount amount amount amount amount amount Examplecomposition (g) (g) (g) (g) (g) (g) (g) (g) (g) (g) Example 60 T1 300280 200 180 150 139 220 201 100 87 Example 61 T2 320 300 200 184 170 153225 197 94 74 Example 62 T3 280 250 170 152 140 127 203 170 88 64Comparative T′-1 20 18 21 18 20 17 23 20 10 6 Example 88 ComparativeT′-2 23 19 21 18 20 16 22 18 11 5 Example 89 Comparative T′-3 22 15 2017 19 15 21 15 10 4 Example 90 Comparative T′-4 24 14 19 17 16 14 20 1412 4 Example 91 Comparative T′-5 10 4 15 7 8 8 11 5 10 5 Example 92Comparative T′-6 5 2 2 1 2 1 2 1 1 1 Example 93 Comparative T′-7 15 7 2011 12 4 18 9 12 7 Example 94

Example 63

740 Grams of a mixed solvent of phenoxyethanol/allethrin (orempenthrin)=50/50 was added to 100 g of a polymer solution (polymerconcentration: about 42%) substituted with imidazolinium cationsobtained as in Example 4 to dissolve the polymer, to obtain a solutionhaving the polymer concentration of 5%. To 100 g of this mixed solutionwas added 0.5 g of the polyglycerolpolyglycidyl ether (described-above)used in Example 4, this was placed into a 100 ml sample bottle, thesample bottle was sealed, and heated for 1 hour in a constanttemperature bath at 70° C. to gelate the material, to obtain anintegrated gelated-type insecticidal composition (TC1).

Comparative Example 95

According to the same manner as that of Comparative Example 7 exceptthat a mixed solvent of phenoxyethanol/allethrin or empenthrin)=50/50was used in place of γ-butyrolactone as a solvent, the comparativeintegrated gelated-type insecticidal composition (TC′-1) was obtained.

Comparative Example 96

According to the same manner as that of Comparative Example 22 exceptthat a mixed solvent of phenoxyethanol/allethrin (or empenthrin)=50/50was used in place of ethanol/water=50/50, the comparative integratedgelated-type insecticidal composition (TC′-2) was obtained.

Regarding the integrated gelated-type insecticidal composition (TC-1) ofExample 63, and comparative integrated gelated-type insecticidalcompositions (TC′-1) and (TC′-2) of Comparative Examples 95 and 96,gelated states immediately after preparation and after with time weremeasured as described above. The results are shown in Table 26. TABLE 26Integrated gelated- Gelated status type Polymer Immediately insecticidalInsecticide concentration after After composition solution (%)preparation with time Example 63 TC1 Phenoxyethanol/ 5 ⊚ ⊚ ComparativeTC′-1 allethrin (or Δ X Example 95 empenthrin) = Comparative TC′-2 50/50◯ X Example 96

Examples 64 to 66

Transfurfurin mixed solvents described in Table 27 were absorbed in thenon-aqueous absorbent sheets (D1), (D2) and (D4) obtained in Examples 6,7 and 9 to obtain the sheet-type insecticidal compositions (TD1) to(TD3) of the present invention.

Comparative Examples 97 to 99

Transfurfurin mixed solvents described in Table 27 were absorbed in thesheets used in Comparative Examples 12 and 13 and the sheet (BD′-3)obtained in Comparative Examples 25 to obtain the comparative sheet-typeinsecticidal compositions (TD′-1) to (TD′-3).

Regarding the sheet-type insecticidal compositions (TD1) to (TD3) ofExample 64 to 66, and the sheet-type insecticidal compositions (TD′-1)to (TD′-3) of Comparative Examples 97 to 99, a liquid absorbing amountand a liquid holding amount were measured as in the aforementionedliquid absorbing amount and liquid holding amount. The results are shownin Table 27. TABLE 27 Mixture of methanol/ Mixture of IPA/ Mixture ofethanol/transfurfurin transfurfurin transfurfurin 50/50 75/25 25/7550/50 50/50 Liquid Liquid Liquid Liquid Liquid Liquid Liquid LiquidLiquid Liquid Sheet-type absorbing holding absorbing holding absorbingholding absorbing holding absorbing holding insecticidal amount amountamount amount amount amount amount amount amount amount Examplecomposition (g) (g) (g) (g) (g) (g) (g) (g) (g) (g) Example 64 TD1 70 5860 52 55 49 60 54 50 41 Example 65 TD2 35 30 30 24 25 22 30 27 25 20Example 66 TD3 60 50 54 35 45 32 125 120 53 39 Comparative TD′-1 2 1 2 12 1 2 1 2 1 Example 97 Comparative TD′-2 2 1 2 1 2 1 2 1 1 1 Example 98Comparative TD′-3 12 8 11 7 10 5 15 10 10 4 Example 99

Example 67

The non-aquous absorbent (B1) obtained in Example 1 was uniformly spreadon a laminate film of rayon non-woven fabric (100 g/m²)/polyethylenefilm (20 μm)/thin paper (16 g/m²) at a rate of 400 g/m², an oilresistant paper (45 g/m²) was overlaid thereon, cut into 23 mm×35 mmsquare, heat-sealed, immersed in a pyrethroid insecticidal ingredientsolution [allethrin (or empenthrin)/phenoxyethanol=50/50] for 3 hours,and then, an excessive amount of the pyrethorid insecticidal ingredientsolution was extracted to obtain the insecticide (U1) of the presentinvention.

Example 68

The non-aqueous absorbent sheet (D1) obtained in Example 6 was immersedin a pyrethroid insecticidal ingredient solution [allethrin (orempenthrin)/phenoxyethanol=50/50] for 3 hours, and an excessive amountof the pyrethroid insecticidal ingredient solution was extracted toobtain the insecticide (U2) of the present invention.

Example 69

The integrated gelated-type insecticidal composition (TC1) of Example 63was adopted as insecticide (U3) of the present invention.

Comparative Examples 100 to 103

According to the same manner as that of Example 67 except that theinsecticidal composition (T′-1) of Comparative Example 88, thesheet-type insecticidal composition (TD′-1) of Comparative Example 97,the integrated gelated-type insecticidal composition (TC′-2) ofComparative Example 96 or Oleosoap PW-190 (manufactured by NipponShokubai Co., Ltd.) was used in place of the non-aqueous absorbent (B1),comparative insecticides (U′-1) to (U′-4) were obtained.

Regarding the insecticides (U1) to (U3) of the present invention and thecomparative insecticides (U′-1) to (U′-4), a normal temperaturevolatilization test, a heating release test and an insecticidal effecttest were performed by the following methods.

[Normal Temperature Volatilization Test]

A packing bag of an internal size of 155 mm×210 mm comprising a filmobtained by laminating a KOP film (polypropylene coated withpolyvinylidene chloride) and a LLDPE film (straight low densitypolyethylene) was prepared, the above-obtained insecticides of Examples67 to 69, and Comparative Examples 100 to 103 were accommodated in eachpacking bag, and heat-sealed. The thus obtained packing bag containingan insecticide was allowed to stand in a constant temperature bath at25° C., and the concentration of an empenthrin steam in the packing bagwas measured by the following method after 1, 10, 30, 60 and 90 day fromallowing to stand.

Empenthrin was measured using gas chromatography. The measuringconditions were the same as those for the aforementioned measurement ofan ethanol steam.

The results are shown in Table 28. In Table 28, the concentration ofempenthrin is expressed by %. TABLE 28 Lapsed days Insecticide Initial10 days 30 days 60 days 90 days Example 67 U1 0.32 0.55 0.54 0.49 0.45Example 68 U2 0.50 0.52 0.60 0.57 0.54 Example 69 U3 0.45 0.75 0.73 0.650.59 Comparative U′-1 0.10 0.05 0.03 0.02 0.01 Example 100 ComparativeU′-2 0.15 0.11 0.08 0.05 0.03 Example 101 Comparative U′-3 0.18 0.140.10 0.08 0.05 Example 102 Comparative U′-4 0.40 0.45 0.44 0.38 0.32Example 103[Heating Release Test]

Each of insecticides of Examples 67 to 69, and Comparative Examples 100to 103 was filled into an aluminum container having a size of a bottomof 23 mm×35 mm and a height of 10 mm, thereafter, the aluminum containerwas placed on a heating release apparatus provided with a radiatingplate of a size of 24 mm×36 mm having a central part heated at 90° C.,and release performance was measured. For measuring an insecticidalingredient, the insecticidal ingredient was trapped with a column filledwith silica gel every predetermined time, the insecticidal ingredientwas extracted with acetone, and then, analyzed under the same conditionsas those for the aforementioned gas chromatography to obtain a releasedamount of the allethrin insecticidal ingredient per time. A value shownin Table 29 is expressed by a relative ratio, letting an initial valueof each preparation to be 1.00. TABLE 29 Lapsed days Insecticide Initial10 days 20 days 30 days 60 days Example 67 U1 1.00 1.00 1.00 0.99 0.97Example 68 U2 1.00 1.00 0.99 0.97 0.95 Example 69 U3 1.00 1.00 0.98 0.960.94 Comparative U′-1 1.00 0.95 0.91 0.90 0.62 Example 100 ComparativeU′-2 1.00 0.51 0.31 0.11 0.03 Example 101 Comparative U′-3 1.00 0.720.54 0.35 0.20 Example 102 Comparative U′-4 1.00 0.93 0.92 0.91 0.65Example 103[Insecticidal Test](Insecticidal Test of Empenthrin by Normal Temperature Volatilization)

Each of insecticides of Examples 67 to 69, and Comparative Examples 100to 103 was placed into a container having an inner volume of about 10Land equipped with a glass lid. Further, 100 clothes moth larvae togetherwith a wool were placed into an about 1L stainless container, this wasaccommodated into the container equipped with a glass lid, and allowedto stand in a constant temperature constant humidity bath retained at25° C. ·70% RH, and the number of clothes moth larvae which died 1, 5,10, 20 and 30 days later was measured. The results are shown in Table30. TABLE 30 Lapsed days Insecticide Initial 5 days 10 days 20 days 30days Example 67 U1 10 90 100 100 100 Example 68 U2 15 95 100 100 100Example 69 U3 12 92 100 100 100 Comparative U′-1 5 10 14 18 21 Example100 Comparative U′-2 1 4 5 6 7 Example 101 Comparative U′-3 5 20 30 3540 Example 102 Comparative U′-4 10 40 60 70 80 Example 103(Insecticidal Test of Allethrin by Heating Release)

Insecticides of Examples 67 to 69, and Comparative Examples 100 to 103were assessed for knock down effect against a common gnat everypredetermined time by the following continuous airing method. A valueshown in Table 31 is expressed by a relative effective ratio of thenumber of a common gnat knocked down by the test sample, letting aninitial value of the number of a common gnat knocked down by a one daymat containing 40 mg of dl, d-cis, trans-allethrin (previous mat) to be1.00.

Continuous airing method: Plastic cylinders having an internal diameterof 20 cm and a height of 43 cm were piled in two layers, a cylinderhaving an internal diameter of 20 cm and a height of 20 cm which isdivided into an upper part and a lower part with a wire net having asieve opening of 1 mm (place for housing a test mosquito) is placedthereon, and a cylinder having an internal diameter of 20 cm and aheight of 20 cm is placed thereon. These 4-layered cylinders were placedon a stand, a heating release apparatus is placed on a center of astand, about 20 test mosquitoes are released in a test cylinder, and thenumber of knocked out mosquitoes is observed with time. Twenty minutesafter exposure, all test mosquitoes are transferred to a cleanpolyethylene container, a 3% aqueous sugar is given, and a rate of deadinsects is examined after 24 hours storage. TABLE 31 Lapsed days 10 2030 60 Insecticide Initial days days days days Example 67 U1 1.48 1.451.44 1.38 1.21 Example 68 U2 1.45 1.40 1.37 1.30 1.15 Example 69 U3 1.471.41 1.32 1.21 1.12 Comparative U′-1 1.24 1.15 1.08 1.02 0.51 Example100 Comparative U′-2 1.49 0.53 0.23 0.12 0.03 Example 101 ComparativeExample 102 U′-3 1.29 0.87 0.52 0.28 0.15 Comparative Example 103 U′-41.24 1.17 1.13 1.12 0.52

From Table 25 to Table 31, the following is apparent.

(1) The insecticidal composition of the present invention has aremarkably higher liquid absorbing amount and liquid holding amount foran organic solvent such as ethanol, methanol, phenoxyethanol and thelike containing a pyrethroid insecticidal ingredient as compared withthe comparative insecticidal compositions.

(2) In the integrated gelated-type insecticidal composition of thepresent invention, a gel containing an organic solvent such as ethanolor the like containing a pyrethroid insecticide has a high strength andis firm even at the low concentration of a non-aqueous absorbent, and isremarkably excellent in stability with time, as compared with thecomparative integrated gelated-type insecticidal compositions.

(3) The insecticide of the present invention exerts the equal orsuperior volatilization or release rate of an insecticidal ingredient ascompared with the previous insecticides. Further, regarding theinsecticidal effect, the insecticide of the present invention can exertperformance equal to or superior over that of the previous products overa long term.

(Fuel Batteries Using Fuel Stores)

Example 70

A gel-like fuel store in which 1 g of the non-aqueous absorbent in thefuel store (BA1) obtained in Example 10 had absorbed a 50% aqueousmethanol solution to saturate, was accommodated in an aluminum can, atleast a part of which was provided with a fuel supply valve (methanolgas permeability of 0.0001 g/m² under RH50%, 40° C. and 24 hours), toobtain the fuel store (H1) of the present invention.

Example 71

According to the same manner as that of Example 70 except that thesheet-type fuel store (BD1) obtained in Example 14 was cut into 5×5 cm,and four pieces were used in place of the non-aqueous absorbent in thefuel store (H1), the fuel store (H2) of the present invention wasobtained.

Example 72

According to the same manner as that of Example 70 except that theintegrated gelated-type fuel store (BC4) obtained in Example 13 was usedin place of the non-aqueous absorbent in the fuel store (H1) and a 50%aqueous methanol solution, the fuel store (H3) of the present inventionwas obtained.

Comparative Example 104

According to the same manner as that of Example 70 except that thenon-aqueous absorbent in the fuel store (BA′-1) of Comparative Example14 was used in place of the non-aqueous absorbent in the fuel store(H1), the comparative fuel store (H′-1) was obtained.

Comparative Example 105

According to the same manner as that of Example 70 except that thesheet-type fuel store (BD′-1) of Comparative Example 23 was cut into 5×5cm, and four pieces were used in place of the non-aqueous absorbent inthe fuel store (H1), the comparative fuel store (H′-2) was obtained.

Comparative Example 106

According to the same manner as that of Example 70 except that the fuelstore (BC′-8) of Comparative Example 22 was used in place of thenon-aqueous absorbent in the fuel store (H1) and a 50% aqueous methanolsolution, the comparative fuel store (H′-3) was obtained.

Comparative Example 107

Separately, in order to prepare a fuel store, according to the methoddescribed in Example of JP-B No. 4-13828, 1 g of dextrin was dissolvedin 5 g of distilled water, and 10 g of methanol was added thereto toobtain powders. The powders were accommodated in an aluminum candescribed in Example 70 to obtain the comparative fuel store (H′-4).

Comparative Example 108

According to the same manner as that of Example 70 except that a bagmade of a polypropylene non-woven fabric (methanol gas permeability of15.0 g/m² under RH50%, 40° C. and 24 hours) was used in place of thealuminum can, the comparative fuel store (H′-5) was obtained.

Regarding the fuel stores (H1) to (H3) of the present invention ofExamples 70 to 72 and the fuel stores (H′-1) to (H′-5) of ComparativeExamples 104 to 108, a volatilization test of liquid fuel and adischarge test were performed by the following methods. The results areshown in Table 32.

[Volatilization Test of Liquid Fuel for Fuel Battery]

Each fuel store was heated to 40° C., decrease in a weight of the fuelstore was measured to obtain an amount of the volatilized liquid fuel,and a remaining weight rate of the liquid fuel was obtained by thefollowing equation.Remaining weight rate (%)=(weight of fuel store before heating/weight offuel store after heating)×100[Discharge Test]

A mixture containing 30 parts by weight of platinum black and 3.5 partsby weight of polytetrafluoroethylene was coated on a platinum net, andfired at 300° C. for 30 minutes in nitrogen gas to prepare an anode(fuel electrode). Separately, a mixture containing 30 parts by weight ofplatinum black and 7.5 parts by weight of polytetrafluoroethylene wascoated on a platinum net, a porous sheet of polytetrafluoroethylene(waterproofing membrane) was overlaid on one side of the coated net,this was pressed at a pressure of 300 kg/cm², and baked at a temperatureof 300° C. for 30 minutes in nitrogen to prepare a cathode (airelectrode). Then, using the aforementioned both electrodes, a cationexchange membrane (Nafion425 manufactured by Du Pond) as a separator,and a 1.5 mol/l aqueous sulfuric aced solution as an electrolytesolution, a fuel battery provided with a line for sending a fuel to ananode and a fuel supply port was prepared.

Each of the fuel stores of Examples 70 to 72, and Comparative Examples104 to 108 was mounted in the fuel supply port, a fuel supply valve wasopened while pressing the fuel store, a fuel battery was operated at adischarge current density of 40 mA/cm² and at an operation temperatureof room temperature, and a discharge time was measured. In addition, thepresence or the absence of fuel leakage after operation was confirmedvisually, and assessed by the following criteria. TABLE 32 Remainingweight rate of alcohol fuel (%) Presence or Initiation After 2 After 1After 2 After 3 Discharge absence of Fuel store date weeks month monthsmonths time fuel leakage Example 70 H-1 100 99.99 99.99 99.99 99.99 62hours ◯ Example 71 H-2 100 99.98 99.98 99.97 99.97 58 hours ◯ Example 72H-3 100 99.99 99.99 99.99 99.99 20 hours ◯ Comparative H′-1 100 99.9899.97 99.97 99.96  4 hours X Example 104 Comparative H′-2 100 99.9899.98 99.97 99.97  2 hours X Example 105 Comparative H′-3 100 99.9799.96 99.95 99.95 20 hours X Example 106 Comparative H′-4 100 99.9699.95 99.93 99.93  2 hours Δ Example 107 Comparative H′-5 100 0 0 0 0 45hours ◯ Example 108◯ No fuel leakageΔ Slight leakageX Leaked, and surrounding is polluted.

Example 73

A fuel supply line of the aforementioned fuel battery prepared in theaforementioned discharge test was filled with the non-aqueous absorbentin the fuel store (BA1) of Example 10 and a mixed fuel ofmethanol/water=50/50 to obtain the fuel battery (J1) of the presentinvention.

Comparative Example 109

According to the same manner as that of Example 73 except that thenon-aqueous absorbent in the fuel store (BA1) of Example 10 was notused, the comparative fuel battery (J′-1) was obtained.

Comparative Example 110

According to the same manner as that of Example 73 except that thenon-aqueous absorbent in the fuel store (BA′-1) of Comparative Example14 was used in place of the non-aqueous absorbent in the fuel store(BA1) of Example 10, the comparative fuel battery (J′-2) was obtained.

Regarding the fuel batteries of Example 73, and Comparative Examples 109and 110, the aforementioned discharge test was performed, andthereafter, operation was stopped and, one week later, re-operation wasperformed. A variation in output at re-operation one week after wasconfirmed, and assessed by the following criteria. The results are shownin Table 33. TABLE 33 Variation in Fuel battery Line filler outputExample 73 J1 H1 ◯ Comparative Example 109 J′-1 None X ComparativeExample 110 J′-2 H′-1 X◯: No variation in outputΔ: Slight variation in outputX: Variation in output

Example 74

The sheet-type fuel store (BD1) of Example 14 was arranged between anelectrode and a cation exchange membrane of the aforementioned fuelbattery prepared for the aforementioned discharge test, to obtain thefuel battery (K1) of the present invention.

Comparative Example 111

According to the same manner as that of Example 74 except that thesheet-type fuel store (BD1) of Example 14 was not used, the comparativefuel battery (K′-1) was obtained.

Comparative Example 112

According to the same manner as that of Example 74 except that thesheet-type fuel store (BD′-1) of Comparative Example 23 was used inplace of the sheet-type fuel store (BD1) of Example 14, the comparativefuel battery (K′-2) was obtained.

Regarding the fuel batteries of Example 74, and Comparative Examples 111and 112, the aforementioned discharge test was performed, and a batteryvoltage at a discharge current of 40 mA/cm, and at a discharge currentof 40 mA/cm² was measured. The results are shown in Table 34. TABLE 34Battery voltage Fuel battery Sheet used (V) Example 74 K1 BD1 0.50Comparative Example 111 K′-1 None 0.35 Comparative Example 112 K′-2BD′-1 0.35

From Tables 32 to 34, the following is apparent.

(1) In the fuel battery of the present invention, since a fuel in a lineis also gelated, there can be provided a fuel battery in which bubblesgeneration during operation stop and bubbles generation due toexothermic heat at operation do not occur, and a fuel supply amount isstable even at re-operation.

(2) Since the fuel battery of the present invention is provided with thesheet-type fuel store of the present invention, crossover of methanolcan be prevented, and deterioration in properties of an air electrodecan be prevented. For this reason, there can be provided a highperformance fuel battery in which a battery voltage is not reduced.

Industrial Applicability

The non-aqueous absorbent of the present invention exerts the followingeffects.

(i) Since the non-aqueous absorbent of the present invention has aremarkably higher liquid absorbing amount for various organic solventsas compared with previous non-aqueous absorbents, the absorbent cangelate a large amount of an organic solvent by addition of an extremelysmall amount. In addition, since the non-aqueous absorbent of thepresent invention also has a high liquid holding amount, the absorbentdoes not release an absorbed organic solvent even when some slightpressure is applied.

(ii) Since the non-aqueous absorbent sheet of the present invention hasa remarkably higher liquid absorbing amount and liquid holding amountfor organic solvents as compared with the previous sheets, and hardlyreleases an absorbed organic solvent even when a pressure is appliedmore or less, the sheet can absorb/hold a large amount of organicsolvent in a short time even when a thickness of a sheet or a total areais small.

(iii) Since when the non-aqueous absorbent sheet of the presentinvention is used as an electrode solution leakage-preventing sheet forsuch as an organic solvent system battery or a condenser, even anextremely thin sheet having a small area can absorb/hold a large amountof organic solvent in a short time, and has low strike-through, there isno possibility that, when leakage of an electrolyte solution occurs, anelectrolyte solution does not pollute other part, or is exposed to theoutside.

(iv) The non-aqueous gel of the present invention is such that anon-aqueous absorbent and an organic solvent are integrated, and can besufficiently applied to package less utilities such as a solid fuel anda gel battery.

(v) Further, since the non-aqueous gel of the present invention has ahigh strength and is firm when a pure content of a crosslinked body islow, and can be gelated even in a system containing a large amount of anelectrolyte such as a lithium ion, a gel having high electricalconductivity can be obtained.

(vi) Moreover, since a non-aqueous gel comprising a non-aqueousabsorbent comprising a crosslinked body and an organic solvent isextremely stable for a long term, there is no fear that a gel isdeteriorated, and an electrolyte solution and the like is exposed.

In addition, the similar effect can be exerted in various utilitiesusing the aforementioned non-aqueous absorbent.

(vii) A non-aqueous absorbent in the alcohol-based bactericidalmaterial, the cold insulating material, the gel sheet for cooling, thefuel composition and the solid fuel using the same, the fragrancematerial, the patch material, the insecticidal composition, the fuelstore and the fuel battery using the same of the present invention doesnot release an absorbed alcohol solvent, fuel battery fuel, aromaticdrug, percutaneous absorption drug, pyrethroid insecticidal ingredientor the like even when a pressure is applied more or less. Therefore, theeffects (disinfectant•sterilization effect, cold insulating effect,combustion time, aroma effect, inflammatory•analgesic effect,insecticidal effect, long term discharge etc.) can be maintained over along term.

(viii) Since the sheet-type alcohol-based bactericide, cool insulator,gel sheet for cooling, fuel composition and solid fuel using the same,fragrance, patch, insecticide, fuel store and fuel battery using thesame have a remarkably higher liquid absorbing amount for an alcoholsolvent, a fuel battery fuel, an aromatic drug, a percutaneousabsorption drug, a pyrethroid insecticidal ingredient and the like ascompared with the previous sheets, and hardly discharge theaforementioned liquid even when a pressure is applied more or less, theycan absorb a large amount of alcohol solvent in a short time even when athickness of a sheet or a total area is small. For this reason, itbecomes possible to prepare a bactericide, a fragrance, a patch, aninsecticide or the like in a short time, and the effect thereof can bemaintained for a long term. In addition, since strike-through propertyof a sheet is low when the sheet-type alcohol-based bactericide is usedas a food storage sheet, there is no fear that an alcohol solventpollutes other part, or is exposed to the outside. The gel sheet forcooling retains sufficient softness even under low temperature statusand, even when taken out from a refrigerator, the sheet can be used asit is.

(ix) Since the non-aqueous absorbent in the present invention and analcohol solvent, a fuel battery fuel, an aromatic drug, a percutaneousabsorption drug, or a pyrethroid insecticidal ingredient can be used toprepare an integrated gel, the present invention can be sufficientlyapplied to the aforementioned package less various molded productutilities. In addition, in the case of fuel battery, the presentinvention can sufficiently satisfy a demand of miniaturization andenhanced performance.

(x) Moreover, since the integrated gelated-type alcohol-basedbactericide, cool insulator, solid fuel, fuel store and fuel batteryusing the same, fragrance, patch and insecticide comprising thenon-aqueous absorbent and the aforementioned solvent or drug areextremely stable for a long term, there is no fear that a gel isdeteriorated, and the aforementioned liquid is exposed.

(xi) Since the aforementioned various molded products in which thepresent alcohol-based bactericidal material and/or alcohol-basedbactericide, cold insulating material and/or cold insulator, gel sheetfor cooling, fuel composition and solid fuel using the same, fuel storeand fuel battery using the same, fragrance material and/or fragrance,patch material and/or patch, insecticidal composition and/or insecticideis accommodated in an external material, at least a part of whichcomprises a steam permeable substrate, have a regulated steam permeationamount, they release a steam of the aforementioned solvent or drug overa long term, they can be suitably used in various utilities for a longterm. In addition, the gel sheet for cooling can provide a gel sheet forcooling which is excellent in contact feeling and softness at a lowtemperature, and easily adhere to a human body. Since when this fuelstore is used as a fuel for a fuel battery, volatilization of a fuelsteam from the surface can be prevented, it becomes possible to retain afuel store for a long term and, since there is no fear of fuel leakage,handling becomes dramatically easy and, since there is no fear of fuelleakage after operation of a fuel battery, this is suitable as a fuelfor a small fuel battery which is conveniently portable.

(xii) Since a body of the fuel battery of the present invention can becompacted, there is no fear of fuel leakage and long term operation ispossible, the fuel battery of the present invention is suitable as aportable fuel battery. Since the fuel battery having a fuel supply lineprovided with the non-aqueous absorbent of the present invention canprevent generation of bubbles due to exothermic heat at long termoperation stoppage or battery operation, a fuel supply amount can bemaintained constant, and a fuel battery having no variation in outputcan be provided. Since the fuel battery having an electrolyte layerprovided with the non-aqueous absorbent of the present invention canprevent crossover of methanol, reduction in properties of an airelectrode can be prevented and, therefore, a high performance fuelbattery can be provided.

1. A non-aqueous absorbent (B) comprising a crosslinked polymer (1)(A)which contains 20 to 100% by weight of a structural unit having acarboxyl group and/or a sulfonate group in its molecule, and in whichfrom 30 to 100% by mol of protons of the carboxyl group and/or thesulfonate group have been substituted with onium cations.
 2. Thenon-aqueous absorbent (B) according to claim 1, wherein the onium cationis a quaternary ammonium cation.
 3. The non-aqueous absorbent (B)according to claim 1, wherein the onium cation is one or more selectedfrom the group consisting of an aliphatic ammonium cation, animidazolinium cation and an imidazolinium cation.
 4. The non-aqueousabsorbent (B) according to claim 1, wherein a content of the structuralunit having a carboxyl group and/or a sulfonate group of the polymer (1)is 40 to 100% by weight, and 50 to 100% by mol of protons of thecarboxyl group and/or the sulfonate group have been substituted withonium cations.
 5. The non-aqueous absorbent (B) according to claim 1,wherein the substitution with onium cations in said crosslinked polymer(A) is performed before or after polymerization of the polymer (1). 6.The non-aqueous absorbent (B) according to claim 1, wherein an amount ofholding an organic solvent selected from propylene carbonate,γ-butyrolactone, ethanol and methanol is 10 g/g to 1,000 g/g.
 7. Anon-aqueous gel (C), which comprises the non-aqueous absorbent (B)according to claim 1 and an organic solvent (2).
 8. The non-aqueous gel(C) according to claim 7, wherein the organic solvent (2) is one or moreselected from the group consisting of an alcohol organic solvent, aglycol organic solvent, a carbonate organic solvent, a ketone organicsolvent, an ether organic solvent, an aliphatic hydrocarbon organicsolvent, an aromatic hydrocarbon organic solvent, a carboxylic acidester organic solvent, a lactone organic solvent and a lactam organicsolvent.
 9. The non-aqueous gel (C) according to claim 7, wherein apolymer (1) which contains 20 to 100% by weight of a structural unithaving a carboxyl group and/or a sulfonate group in its molecule and inwhich from 30 to 100% by mol of protons of the carboxyl group and/or thesulfonate group have been substituted with onium cations is dissolved inthe organic solvent (2), and is crosslinked using one or morecrosslinking means selected from the group consisting of crosslinkingwith a crosslinking agent, crosslinking by irradiation withultraviolet-ray or radiation, and crossliking by heating.
 10. Thenon-aqueous gel (C) according to claim 7, wherein the gel is obtained bypolymerizing 20 to 100% by weight of a monomer which contains a carboxylgroup and/or a sulfonate group, and in which from 30 to 100% by mol ofprotons of the carboxyl group and/or the sulfonate group have beensubstituted with onium cations and, if necessary, 0 to 80% by weight ofother copolymerizable monomer, in the organic solvent (2) in thepresence of a crosslinking agent.
 11. A non-aqueous absorbent sheet (D),which comprises the non-aqueous absorbent (B) according to claim 1, anda substrate selected from the group consisting of a non-woven fabric, awoven fabric, a paper and a film.
 12. The non-aqueous absorbent sheet(D) according to claim 11, wherein the polymer (1) which contains 20 to100% by weight of a structural unit having a carboxylic acid groupand/or a sulfonate group in its molecule, and in which from 30 to 100%by mol of protons of the carboxylic acid group and/or the sulfonategroup have been substituted with onium cations, is impregnated intoand/or coated on one or more substrates selected from the groupconsisting of a non-woven fabric, a woven fabric, a paper and a film,and thereafter is crosslinked using one or more crosslinking meansselected from the group consisting of crosslinking with a crosslinkingagent, crosslinking by irradiation with ultraviolet-ray or radiation,and crosslinking by heating.
 13. The non-aqueous absorbent sheet (D)according to claim 11, wherein a mixed solution containing 20 to 100% byweight of a monomer which contains a carboxyl group and/or a sulfonicgroup and in which from 30 to 100% by mol of protons of the carboxylgroup and/or the sulfonate group have been substituted with oniumcations, 0 to 80% by weight of other copolymerizable monomer, and acrosslinking agent is impregnated into and/or coated on one or moresubstrates selected from the group consisting of a non-woven fabric, apaper, a woven fabric and a film, and thereafter the substrate ispolymerized using one or more means selected from the group consistingof use of a polymerization initiator, irradiation with ultraviolet-rayor radiation, and heating.
 14. A non-aqueous absorbent (E) characterizedin that a shape of the non-aqueous absorbent (B) according to claim 1 isa particle having an average particle diameter of 1 to 5,000 μm.
 15. Thenon-aqueous absorbent (B) according to claim 1, which is used as aconstitutional material for an alcohol-based bactericidal material or analcohol-based bactericide, a cool insulating material or a coolinsulator, a gel sheet for cooling, a fuel composition for solid fuelsor a solid fuel using the same, a fragrance material or a fragrance, apatch material or a patch, an insecticidal composition or aninsecticide, or a fuel store for fuel batteries or a fuel battery usingthe same.
 16. An alcohol-based bactericidal material or an alcohol-basedbactericide, a cool insulating material or a cool insulator, a gel sheetfor cooling, or a fuel composition for solid fuels or solid fuel usingthe same, which comprises the non-aqueous absorbent (B) according toclaim 1 and an alcohol solvent.
 17. A fragrance material or a fragrance,which comprises the non-aqueous absorbent (B) according to claim 1 andan aromatic drug.
 18. A patch material or a patch, which comprises thenon-aqueous absorbent (B) according to claim 1 and a percutaneousabsorption drug.
 19. An insecticidal composition or an insecticide,which comprises the non-aqueous absorbent (B) according to claim 1 and apyrethroid insecticidal ingredient.
 20. A fuel store for fuel batteriesor a fuel battery using the same, which comprises the non-aqueousabsorbent (B) according to claim 1 and a liquid fuel for fuel batteries.21. A lithium battery characterized in that the non-aqueous absorbent(B) according to claim 1 is used as a gel electrolyte.